Grade 12Energy, rates, equilibrium, acids, cells and solutions

Grade 12 ChemistryStudy Guide

Formulas · worked examples · practice problems with the answer key

Built to Ontario's SCH4U. Also covers most of BC Chemistry 12 and Alberta Chemistry 30.

6 modules · 58 formulas · 80 practice problems

The Exam Room · formula.expert · metric edition 1September 2026 · Mathieu Leclerc, with Claude

About this study guide

Who it’s for. Students working through Grade 12 Chemistry, and the teachers, tutors and parents printing handouts for them. Print it, copy it, staple it: it’s free for classroom use, whole or by the page.

How to use it. Each module teaches its formulas in order (equation, picture, and what every symbol means), then closes with a practice set. Work the problems with a pencil; the answer key waits at the back so honest work gets an honest check. The two-page formula sheet up front is the exam-day companion, and every formula carries its number (Chemistry 12-1 onward) so your written work can cite exactly which one you used.

Do it live. Every problem in here has a living version in the Exam Room at formula.expert/exams/grade-12-chemistry: new numbers every attempt, hints that pop down when you want them, stars and streaks when you don’t need them. When a printed problem stumps you, the matching lesson will coach you through it, step by step, free and with no sign-up. Other courses’ study guides live at formula.expert/study-guides.

Figures

The formula sheet

Module 1 · Thermochemistry

Chemistry 12-1 Moles from Mass (n = m/M)
n=mMn = \frac{m}{M}
Converts a measured mass into an amount of substance by dividing by the molar mass.
Chemistry 12-2 Particles from Moles (Avogadro's Number)
N=n NAN = n\,N_A
Converts an amount in moles into an actual particle count using the Avogadro constant NA =…
Chemistry 12-3 Sensible Heat (Q = mcΔT)
Q=mcΔTQ = m c \Delta T
Heat needed to change a mass's temperature: mass times specific heat times the temperature change.
Chemistry 12-4 Latent Heat
Q=mLQ = m L
Heat absorbed or released when a mass changes phase at constant temperature.
Chemistry 12-5 Heat of Reaction
q=nΔHq = n \Delta H
Scales a reaction's molar enthalpy change by the amount reacted to give the total heat released or…
Chemistry 12-6 Molarity (C = n/V)
C=nVC = \frac{n}{V}
Defines molar concentration as moles of solute per volume of solution.
Chemistry 12-7 Hess's Law (Three-Step Sum)
ΔHrxn=ΔH1+ΔH2+ΔH3\Delta H_{\text{rxn}} = \Delta H_1 + \Delta H_2 + \Delta H_3
Hess's law: the enthalpy change of a target reaction is the sum of the enthalpy changes of the…
Chemistry 12-8 Standard Enthalpy of Reaction from Formation Enthalpies
ΔHrxn∘=∑ΔHf,prod∘−∑ΔHf,react∘\Delta H^{\circ}_{\text{rxn}} = \sum \Delta H^{\circ}_{f,\text{prod}} - \sum \Delta H^{\circ}_{f,\text{react}}
The tabulated form of Hess's law: standard enthalpy of reaction equals the summed formation…

Module 2 · Rates & Kinetics

Chemistry 12-9 Power-Law Reaction Rate
r=k CA nr = k\,C_A^{\,n}
The rate of a reaction as a power of the reactant concentration.
Chemistry 12-10 Arrhenius Equation
k=A e−Ea/RTk = A\,e^{-E_a/RT}
Gives a reaction's rate constant from its activation energy, pre-exponential factor, and absolute…
Chemistry 12-11 Arrhenius Two-Temperature Form
ln⁡k2k1=EaR(1T1−1T2)\ln\frac{k_2}{k_1} = \frac{E_a}{R}\left(\frac{1}{T_1} - \frac{1}{T_2}\right)
Extracts an activation energy from two rate constants measured at two temperatures, eliminating the…
Chemistry 12-12 Activation Energy from an Arrhenius Plot
Ea=−R×slopeE_a = -R \times \text{slope}
Converts the slope of a ln k versus 1/T Arrhenius plot into an activation energy, the standard…
Chemistry 12-13 Zero-Order Integrated Rate Law
[A]=[A]0−kt[\mathrm{A}] = [\mathrm{A}]_0 - kt
Gives the concentration remaining in a zero-order reaction, where the rate is constant and…
Chemistry 12-14 First-Order Integrated Rate Law
[A]=[A]0 e−kt[\mathrm{A}] = [\mathrm{A}]_0\,e^{-kt}
Gives the concentration remaining in a first-order reaction, the exponential decay that governs…
Chemistry 12-15 Half-Life Decay
N=N0(12)t/t1/2N = N_0 \left(\frac{1}{2}\right)^{t/t_{1/2}}
Gives the quantity remaining after repeated halvings over an elapsed time measured in half-lives.
Chemistry 12-16 Half-Life and Decay Constant
t1/2=ln⁡2λt_{1/2} = \frac{\ln 2}{\lambda}
Converts between a half-life and the exponential decay constant via the factor ln 2 = 0.6931471806.
Chemistry 12-17 Second-Order Integrated Rate Law
1[A]=1[A]0+kt\frac{1}{[\mathrm{A}]} = \frac{1}{[\mathrm{A}]_0} + kt
Gives the concentration remaining in a second-order reaction, where the reciprocal of concentration…
Chemistry 12-18 Half-Life of a Second-Order Reaction
t1/2=1k [A]0t_{1/2} = \frac{1}{k\,[\mathrm{A}]_0}
Gives the half-life of a second-order reaction, which unlike a first-order half-life depends on the…

Module 3 · Chemical Equilibrium

Chemistry 12-19 Equilibrium Constant Kc (A + B ⇌ C + D)
Kc=[C][D][A][B]K_c = \frac{[\mathrm{C}][\mathrm{D}]}{[\mathrm{A}][\mathrm{B}]}
Computes the equilibrium constant or reaction quotient for a one-to-one reaction from the four…
Chemistry 12-20 Reaction Quotient Q (aA + bB ⇌ cC)
Q=[C]c[A]a [B]bQ = \frac{[\mathrm{C}]^{c}}{[\mathrm{A}]^{a}\,[\mathrm{B}]^{b}}
Reaction quotient Q from any concentrations, raised to stoichiometric powers: the number you…
Chemistry 12-21 Kp from Kc (Kp = Kc(RT)^Δn)
Kp=Kc(RT)ΔnK_p = K_c (RT)^{\Delta n}
Converts a gas-phase equilibrium constant between pressure and concentration bases using the change…
Chemistry 12-22 Ideal Gas Law
PV=nRTP V = n R T
Relates pressure, volume, amount, and temperature of a gas.
Chemistry 12-23 Solubility Product of a 1:1 Salt
Ksp=s2K_{sp} = s^{2}
Links the solubility product of an AB salt such as AgCl or BaSO4 to its molar solubility, since…
Chemistry 12-24 Solubility Product of an AB₂ Salt
Ksp=4s3K_{sp} = 4s^{3}
Links the solubility product of an AB2 or A2B salt such as CaF2 or Mg(OH)2 to its molar solubility,…
Chemistry 12-25 Gibbs Free Energy Change (ΔG = ΔH − TΔS)
ΔG=ΔH−T ΔS\Delta G = \Delta H - T\,\Delta S
Combines a reaction's enthalpy and entropy changes at a given temperature to decide whether it can…
Chemistry 12-26 Gibbs Free Energy and the Equilibrium Constant
ΔG∘=−RTln⁡K\Delta G^{\circ} = -RT\ln K
Converts between a reaction's standard free energy change and its equilibrium constant, the bridge…

Module 4 · Acids & Bases

Chemistry 12-27 pH from Hydrogen Ion Concentration
pH=−log⁡10 [H+]\mathrm{pH} = -\log_{10}\,[\mathrm{H^+}]
Expresses acidity as the negative base-10 logarithm of the hydrogen ion concentration in mol/L.
Chemistry 12-28 pH and pOH Relation
pH+pOH=14\mathrm{pH} + \mathrm{pOH} = 14
Links the acidity and basicity scales of any aqueous solution at 25 °C, where pKw = 14.
Chemistry 12-29 Ka and Kb Relation through Kw
Ka Kb=KwK_a \, K_b = K_w
Links a weak acid's dissociation constant to that of its conjugate base through the ion product of…
Chemistry 12-30 pKa from Acid Dissociation Constant
pKa=−log⁡10Ka\mathrm{p}K_a = -\log_{10} K_a
Converts an acid dissociation constant into its logarithmic pKa form and back, compressing a huge…
Chemistry 12-31 pKb from Base Dissociation Constant
pKb=−log⁡10Kb\mathrm{p}K_b = -\log_{10} K_b
Converts a base dissociation constant into its logarithmic pKb form and back, the basic-side…
Chemistry 12-32 pH of a Weak Acid from Ka
pH=−log⁡10Ka C\mathrm{pH} = -\log_{10}\sqrt{K_a\,C}
Estimates the pH of a weak monoprotic acid solution from its dissociation constant and formal…
Chemistry 12-33 Percent Ionization of a Weak Acid
% ion=[H+]C×100%\%\,\text{ion} = \frac{[\mathrm{H^+}]}{C} \times 100\%
Expresses what fraction of a weak acid has actually donated its proton, comparing the equilibrium…
Chemistry 12-34 Henderson–Hasselbalch Equation (Weak Acid Buffer)
pH=pKa+log⁡10 ⁣[A−][HA]\mathrm{pH} = \mathrm{p}K_a + \log_{10}\!\frac{[\mathrm{A^-}]}{[\mathrm{HA}]}
Gives the pH of a buffer from the acid's pKa and the ratio of conjugate base to undissociated acid,…
Chemistry 12-35 Henderson–Hasselbalch Equation (Weak Base Buffer)
pOH=pKb+log⁡10 ⁣[BH+][B]\mathrm{pOH} = \mathrm{p}K_b + \log_{10}\!\frac{[\mathrm{BH^+}]}{[\mathrm{B}]}
Gives the pOH of a weak base buffer from the base's pKb and the ratio of conjugate acid to free…
Chemistry 12-36 Dilution Equation (C1V1 = C2V2)
C1V1=C2V2C_1 V_1 = C_2 V_2
States that concentration times volume is conserved when a solution is diluted, since the moles of…
Chemistry 12-37 Titration: Concentration of an Unknown
Ca=n CbVbVaC_a = \frac{n\,C_b V_b}{V_a}
Finds an analyte's concentration from the titre volume, titrant concentration, and the reaction's…

Module 5 · Electrochemistry

Module 6 · Gases & Solutions

Chemistry 12-42 Boyle's Law
P1V1=P2V2P_1 V_1 = P_2 V_2
At constant temperature, pressure times volume stays constant for a fixed amount of gas.
Chemistry 12-43 Charles's Law
V1T1=V2T2\frac{V_1}{T_1} = \frac{V_2}{T_2}
At constant pressure, gas volume is directly proportional to absolute temperature.
Chemistry 12-44 Gay-Lussac's Law
P1T1=P2T2\frac{P_1}{T_1} = \frac{P_2}{T_2}
At constant volume, gas pressure is directly proportional to absolute temperature.
Chemistry 12-45 Combined Gas Law
P1V1T1=P2V2T2\frac{P_1 V_1}{T_1} = \frac{P_2 V_2}{T_2}
For a fixed amount of gas, pressure times volume over absolute temperature stays constant between…
Chemistry 12-46 Gas Volume at STP
V=n VmV = n\,V_m
Converts between moles of an ideal gas and its volume at STP using the molar volume Vm = 22.414…
Chemistry 12-47 Gas Density from Molar Mass
ρ=PMRT\rho = \frac{PM}{RT}
Gives an ideal gas's density from its molar mass, pressure, and absolute temperature using R =…
Chemistry 12-48 Partial Pressure from Mole Fraction
Pi=xi PtotalP_i = x_i \, P_{\text{total}}
Gives a gas component's partial pressure as its mole fraction times the total pressure, the…
Chemistry 12-49 Mole Fraction
x1=n1n1+n2x_1 = \frac{n_1}{n_1 + n_2}
Gives the fraction of all moles in a two-component mixture contributed by the solute.
Chemistry 12-50 Graham's Law of Effusion
r1r2=M2M1\frac{r_1}{r_2} = \sqrt{\frac{M_2}{M_1}}
Relates the effusion rates of two gases to the inverse square root of their molar masses.
Chemistry 12-51 Molality (b = n/m)
b=nmsolventb = \frac{n}{m_{\text{solvent}}}
Defines molality as moles of solute per kilogram of solvent.
Chemistry 12-52 Mass Percent of a Solution
c=msolutemsolution×100%c = \frac{m_{\text{solute}}}{m_{\text{solution}}} \times 100\%
Expresses a solution's concentration as the solute's share of the total solution mass in percent.
Chemistry 12-53 Boiling-Point Elevation
ΔTb=Kb b\Delta T_b = K_b \, b
Gives how far a dissolved solute raises a solvent's boiling point from the molality and the…
Chemistry 12-54 Freezing-Point Depression
ΔTf=Kf b\Delta T_f = K_f \, b
Gives how far a dissolved solute lowers a solvent's freezing point from the molality and the…
Chemistry 12-55 Osmotic Pressure (Π = MRT)
Π=MRT\Pi = M R T
Gives the osmotic pressure of a dilute solution from its molar concentration and absolute…
Chemistry 12-56 Raoult's Law
P=x P0P = x \, P^{0}
Gives the vapour pressure of a solvent above an ideal solution as its mole fraction times the pure…
Chemistry 12-57 Henry's Law (Gas Solubility)
C=H PC = H\,P
At a fixed temperature the concentration a gas reaches in a liquid is proportional to its partial…
Chemistry 12-58 Clausius–Clapeyron Equation (Two-Point Form)
ln⁡ ⁣(P2P1)=−ΔHvapR(1T2−1T1)\ln\!\left(\frac{P_2}{P_1}\right) = -\frac{\Delta H_{vap}}{R}\left(\frac{1}{T_2} - \frac{1}{T_1}\right)
Relates two points on a liquid's vapour-pressure curve to its molar enthalpy of vaporisation,…
Module 1

Thermochemistry

Counting particles · Heat in the cup · Warming and melting · Heat per mole · The coffee cup · The ladder of Hess · The formation shortcut · The Heat Audit

In BC Chemistry 12 · Alberta Chemistry 30 · Ontario SCH4U

(Chemistry 12-1)n=mMn = \frac{m}{M}
Where
  • nn= Amount of substance (mol)
  • mm= Mass (kg)
  • MM= Molar mass (g/mol)
mMn
Figure 1.1: moles from mass (n = m/m).

The mole is chemistry's counting unit: a fixed number of particles large enough to weigh on a bench balance. Dividing a measured mass by the molar mass is the bridge between the two worlds: weigh out 36.0 g of water, divide by its molar mass of 18.02 g/mol, and you know you have 2.00 mol, about 1.2 × 10²⁴ molecules. Every stoichiometry problem starts or ends with this conversion, because balanced equations speak in moles while balances speak in grams.

The word mole was coined by Wilhelm Ostwald in the 1890s, but the idea goes back to Avogadro's 1811 hypothesis that equal gas volumes hold equal numbers of molecules. Since the 2019 SI redefinition, the mole is defined by an exact count, 6.02214076 × 10²³ particles, so molar masses in g/mol are now measured quantities rather than definitions.

Worked example 1.1. Given mm = 116.88 g, MM = 58.44 g/mol; find nn (amount of substance). 116.88 g NaCl (M = 58.44 g/mol) → exactly 2 mol.

1.2 Particles from Moles (Avogadro's Number)

Solve it online →formula.expert/solvers/particles-from-moles
(Chemistry 12-2)N=n NAN = n\,N_A
Where
  • NN= Number of particles
  • nn= Amount of substance (mol)
nN
Figure 1.2: particles from moles (avogadro's number).

A mole is a count and nothing more mysterious: the chemist's dozen, scaled up to something useful. Multiply an amount in moles by the Avogadro constant and you have the literal number of particles in front of you. The only real question is why the constant is that particular size, and the answer is that it was chosen to make the bridge between two worlds land cleanly: NAN_A is the number of atoms that makes a mole of carbon-12 weigh exactly 12 grams. That choice is what lets a mass in grams read off a balance be converted into a count of atoms, which is the single most useful trick in chemistry.

Scale is the thing worth feeling here. A 250 g glass of water is 250/18.015 = 13.9 mol, so it holds 13.9×6.022×1023=8.4×102413.9 \times 6.022\times10^{23} = 8.4\times10^{24} molecules. Now count the other way: all the water on Earth, about 1.4×10211.4\times10^{21} litres, divided into 250 g glasses, comes to roughly 5.4×10215.4\times10^{21} glasses. There are about fifteen hundred times more molecules in one glass of water than there are glasses of water in every ocean on the planet. That ratio is why chemists never think about individual molecules and why statistical behaviour is so reliable at this scale.

The constant carries Avogadro's name but not his arithmetic: he proposed in 1811 that equal gas volumes hold equal numbers of particles, and never estimated the number. Jean Perrin did, from Brownian motion, and named it for Avogadro in 1909, work that took him the 1926 Nobel Prize. The 2019 SI redefinition then reversed the logic entirely. NAN_A is now exact by decree at 6.02214076 × 10²³ per mole, and the mole is defined as that many entities. Carbon-12's role is retired: a mole of it now weighs 12 grams only to within experimental uncertainty, rather than by definition. So 2.00 mol contains exactly 1.204428152 × 10²⁴ particles, with no uncertainty in the constant at all, though your measured 2.00 mol still has its own.

The error that swallows this page whole is leaving "particles of what" unstated. A mole of O₂ is 6.022 × 10²³ molecules but 1.204 × 10²⁴ atoms. A mole of NaCl is 6.022 × 10²³ formula units, which is 6.022 × 10²³ sodium ions plus the same number of chloride ions: 1.204 × 10²⁴ ions in total. A mole of Al₂(SO₄)₃ contains three moles of sulfate. Almost every wrong answer here is a correct calculation attached to the wrong noun, so write the noun down before you multiply: molecules, atoms, ions, or formula units.

Two smaller slips. Dividing a molar mass by NAN_A gives the mass of one particle in grams, water comes out at 2.99×10−232.99\times10^{-23} g, and people routinely lose a factor of 1000 by mixing kilograms into that step, or confuse it with the mass in unified atomic mass units, which is just the molar mass number again with different units. And because NAN_A is exact, it never limits your significant figures; only the amount you measured does.

Worked example 1.2. Given nn = 2 mol; find NN (number of particles). 2 mol → 1.204428152e24 particles.

(Chemistry 12-3)Q=mcΔTQ = m c \Delta T
Where
  • QQ= Heat energy (J)
  • mm= Mass (kg)
  • cpc_p= Specific heat capacity (J/(kg·K))
  • ΔT\Delta T= Temperature change (C°)
mcpQΔT
Figure 1.3: sensible heat (q = mcδt).

Sensible heat is the energy that changes a substance's temperature without changing its phase. The specific heat capacity c is the price of each degree: how many joules one kilogram demands per kelvin of warming. Water's is famously steep at about 4186 J/(kg·K), which is why oceans moderate coastal climates and why a kettle takes its time. Heating 1.5 kg of water from 15 °C to 95 °C costs Q = 1.5 × 4186 × 80 ≈ 502 kJ.

The concept dates to Joseph Black's calorimetry experiments in 1760s Glasgow, which first pried apart the ideas of temperature and heat. Note that ΔT is a temperature difference, so a change of 80 °C equals a change of 80 K exactly: Fahrenheit differences convert by scale alone, with no offset. The formula holds as long as c stays roughly constant over the range and nothing melts or boils along the way.

Worked example 1.3. Given mm = 2 kg, cpc_p = 4186 J/(kg·K), ΔT\Delta T = 30 C°; find QQ (heat energy). 2 kg water, c = 4186, ΔT = 30 C° → 251160 J.

(Chemistry 12-4)Q=mLQ = m L
Where
  • QQ= Heat absorbed or released (J)
  • mm= Mass changing phase (kg)
  • LL= Specific latent heat (J/kg)
QLmm
Figure 1.4: latent heat.

Latent heat is the energy a phase change absorbs or releases while the temperature holds still. Melting 1 kg of ice at 0 °C soaks up 334 kJ, enough to heat that same water from 0 °C to 80 °C, yet the thermometer never moves until the last crystal is gone. Boiling is costlier still: vaporizing a kilogram of water takes about 2256 kJ, more than five times the energy needed to warm it from ice-cold to boiling.

Joseph Black coined the term in 1762: latent means hidden, because the heat disappears into the phase change instead of the temperature reading. The physics runs everyday life: sweat cools you as it evaporates, steam scalds far worse than boiling water because it dumps its latent heat on condensing against skin, and every refrigerator moves heat by evaporating and condensing a working fluid in an endless loop.

One quantity, three notations, depending on whose book you are holding. Physics writes it L, as here, and splits it into Lf for fusion and Lv for vaporization. Engineering and every steam table print it hfg, where f is saturated fluid and g is saturated gas, so hfg = hg − hf is the gap between the two columns, which is exactly why it shrinks to nothing at the critical point where those columns meet. Chemistry writes it as an enthalpy of vaporization per MOLE rather than per kilogram, so its numbers look nothing like these until you divide by the molar mass. Same energy, three addresses.

Worked example 1.4. Given mm = 1 kg, LL = 334 kJ/kg; find QQ (heat absorbed or released). Melting 1 kg ice at 334 kJ/kg → 334000 J.

(Chemistry 12-5)q=nΔHq = n \Delta H
Where
  • qq= Heat released or absorbed (J)
  • nn= Amount of substance (mol)
  • ΔH\Delta H= Molar enthalpy change (kJ/mol)
qΔHn
Figure 1.5: heat of reaction.

Enthalpy is an extensive quantity: run a reaction twice and you get twice the heat. That is the entire justification for q=nΔHq = n\Delta H, and it is why tabulating a single per-mole figure is enough to describe a reaction at any scale from a test tube to a boiler. The sign convention runs from the system's point of view: ΔH negative for an exothermic reaction, because the system's enthalpy falls as heat leaves it. A negative qq is not an error message; it is the answer telling you the heat came out.

Something concrete. Heating 200 L of water from 10 °C to 60 °C takes 200×4.186×50=41 860200 \times 4.186 \times 50 = 41\,860 kJ. Methane burns at ΔH = −890.3 kJ/mol, so the amount required is n=41 860/890.3=47.0n = 41\,860/890.3 = 47.0 mol: about 754 g of methane, or 1.05 m³ at STP, before any consideration of how much of that heat actually reaches the water. Chain those three pages together and you have most of a combustion calculation.

The relation's real power is that enthalpy is a state function, which is Hess's law: the heat of a reaction depends only on where it starts and ends, not on the route. So you can add reactions like algebra, and you can build any ΔH you need from tabulated standard enthalpies of formation, products minus reactants, without ever running the reaction. One caution on what is being measured: ΔH is the heat at constant pressure, which is what an open vessel or a flowing burner delivers. A bomb calorimeter holds volume constant and measures ΔU instead, and the two differ by the work done pushing the atmosphere aside, ΔH=ΔU+ΔngasRT\Delta H = \Delta U + \Delta n_{gas}RT.

The question this page most needs you to ask is "per mole of what?" ΔH belongs to the balanced equation as written, not to any one substance in it. 2H2+O2→2H2O2\text{H}_2 + \text{O}_2 \rightarrow 2\text{H}_2\text{O} has ΔH = −571.6 kJ, but H2+12O2→H2O\text{H}_2 + \tfrac{1}{2}\text{O}_2 \rightarrow \text{H}_2\text{O} has ΔH = −285.8 kJ. Same chemistry, same physical world, different bookkeeping, and a factor of two waiting for anyone who reads a table without reading the equation above it. Write the equation first, decide which species your nn counts, and make the two agree.

Then the trap that costs more marks than any other in stoichiometry. The limiting reagent is found by moles, never by mass. Given 100 g of hydrogen and 100 g of oxygen, the masses are equal and the amounts are not remotely: 49.6 mol of H₂ against 3.13 mol of O₂, and the reaction needs two hydrogens per oxygen. Oxygen limits by a factor of eight, and 100 g of hydrogen looks generous only because hydrogen is light. Convert everything to moles, divide each by its coefficient in the balanced equation, and the smallest quotient is the limiter. The nn that goes into q=nΔHq = n\Delta H is then the extent of reaction that limiter permits, not the amount of whatever you happened to weigh out.

One last note for anyone comparing fuel figures. Combustion enthalpies come in two flavours depending on whether the product water is counted as liquid or as vapour, differing by 44 kJ per mole of water. That is the higher-heating-value and lower-heating-value distinction, and for methane it is about a 10% gap. Two sources can disagree by that much while both being correct.

Worked example 1.5. Given nn = 2 mol, ΔH\Delta H = -890 kJ/mol; find qq (heat released or absorbed). 2 mol CH4 at dH = -890 kJ/mol → q = -1780 kJ.

(Chemistry 12-6)C=nVC = \frac{n}{V}
Where
  • CC= Molar concentration (M)
  • nn= Amount of solute (mol)
  • VV= Volume of solution (L)
VCn
Figure 1.6: molarity (c = n/v).

Molarity answers the practical question "how much stuff is in this bottle?" by counting moles of solute per liter of solution. Dissolve 58.44 g of table salt, exactly one mole of NaCl, in water and top up to the 1.00 L mark of a volumetric flask, and you have a 1.00 M solution. Note the fine print: it is per liter of solution, not per liter of water added, which is why chemists fill to a calibrated mark instead of adding a measured liter of solvent.

Molarity is the workhorse concentration unit because reactions are mole-to-mole affairs: multiplying C by a dispensed volume immediately gives the moles delivered, which is exactly what a titration calculation needs. Physiological saline is about 0.154 M NaCl, ocean water roughly 0.5 M, and concentrated hydrochloric acid around 12 M: a span that dilution calculations cross daily in every lab.

Worked example 1.6. Given nn = 2 mol, VV = 4 L; find CC (molar concentration). 2 mol in 4 L → 0.5 mol/L.

(Chemistry 12-7)ΔHrxn=ΔH1+ΔH2+ΔH3\Delta H_{\text{rxn}} = \Delta H_1 + \Delta H_2 + \Delta H_3
Where
  • ΔHrxn\Delta H_{\text{rxn}}= Enthalpy change of the target reaction (kJ/mol)
  • ΔH1\Delta H_1= Enthalpy change of step 1 (kJ/mol)
  • ΔH2\Delta H_2= Enthalpy change of step 2 (kJ/mol)
  • ΔH3\Delta H_3= Enthalpy change of step 3 (kJ/mol)
ΔH1ΔH2ΔH3ΔHrxn
Figure 1.7: hess's law (three-step sum).

Enthalpy is a state function: it depends only on where the chemistry starts and where it ends, never on the route. So if you can reach the target reaction by adding up a chain of steps whose enthalpies you already know, their sum is the answer. Reverse a step and you flip the sign of its ΔH; double a step and you double its ΔH. Only two steps? Enter 0 for the third.

Germain Henri Hess published this in 1840 in St Petersburg, and the date is the remarkable part: it is before the first law of thermodynamics was stated. Joule's paddle-wheel measurements, Mayer's paper, and Helmholtz's 1847 formulation of energy conservation were all still to come. Hess had no theory of energy conservation to lean on; he simply measured heats of neutralisation with a calorimeter, noticed that the totals were the same whichever order he ran the reactions in, and stated the constancy of heat summation as an empirical law. It later turned out to be a corollary of the first law, which is a fair definition of a good experimentalist.

Worked case: the enthalpy of formation of acetylene cannot be measured directly, you cannot make 2C(s) + H₂(g) → C₂H₂(g) happen in a calorimeter, but its combustion can. Route it: 2C + 2O₂ → 2CO₂ at 2(−393.5) = −787.0 kJ/mol; H₂ + ½O₂ → H₂O at −285.8 kJ/mol; and the reversed combustion 2CO₂ + H₂O → C₂H₂ + 5/2 O₂ at +1299.6 kJ/mol. Sum: −787.0 − 285.8 + 1299.6 = +226.8 kJ/mol, matching the tabulated +227 kJ/mol. Acetylene is one of the few hydrocarbons with a positive formation enthalpy, which is exactly why an oxy-acetylene torch burns hot enough to cut steel.

Worked example 1.7. Given ΔH1\Delta H_1 = -787.0 kJ/mol, ΔH2\Delta H_2 = -285.8 kJ/mol, ΔH3\Delta H_3 = 1299.6 kJ/mol; find ΔHrxn\Delta H_{\text{rxn}} (enthalpy change of the target reaction). Acetylene formation: -787.0 - 285.8 + 1299.6 → +226.8 kJ/mol.

1.8 Standard Enthalpy of Reaction from Formation Enthalpies

Solve it online →formula.expert/solvers/hess-law-formation-enthalpies
(Chemistry 12-8)ΔHrxn∘=∑ΔHf,prod∘−∑ΔHf,react∘\Delta H^{\circ}_{\text{rxn}} = \sum \Delta H^{\circ}_{f,\text{prod}} - \sum \Delta H^{\circ}_{f,\text{react}}
Where
  • ΔHrxn∘\Delta H^{\circ}_{\text{rxn}}= Standard enthalpy of reaction (kJ/mol)
  • ∑ΔHf,prod∘\sum \Delta H^{\circ}_{f,\text{prod}}= Sum of product formation enthalpies (kJ/mol)
  • ∑ΔHf,react∘\sum \Delta H^{\circ}_{f,\text{react}}= Sum of reactant formation enthalpies (kJ/mol)
ΣΔHf,reactΣΔHf,prodΔH°rxn
Figure 1.8: standard enthalpy of reaction from formation enthalpies.

This is Hess's law with the bookkeeping already done for you. Every compound gets one tabulated number (the enthalpy of forming one mole of it from its elements in their standard states) and every element in its standard state is defined as exactly zero. Build any reaction out of "unmake the reactants back to elements, then make the products", and the whole route collapses to products minus reactants. Multiply each ΔH°f by its coefficient in the balanced equation before you add: the sums that go into this calculator are already coefficient-weighted.

The two classic slips are the minus sign and the physical state. Reactants are subtracted, so a strongly negative reactant enthalpy pushes ΔH°rxn up, not down. And ΔH°f depends on state: liquid water is −285.8 kJ/mol but water vapour is −241.8 kJ/mol, a 44 kJ/mol gap that is exactly the enthalpy of vaporisation and the entire difference between a fuel's higher and lower heating value.

Worked case: burning methane, CH₄ + 2O₂ → CO₂ + 2H₂O(l). Products: −393.5 + 2(−285.8) = −965.1 kJ/mol. Reactants: −74.6 + 2(0) = −74.6 kJ/mol, since O₂ is an element in its standard state. ΔH°rxn = −965.1 − (−74.6) = −890.5 kJ/mol, the number a gas utility is selling you, one mole at a time.

Worked example 1.8. Given ∑ΔHf,prod∘\sum \Delta H^{\circ}_{f,\text{prod}} = -965.1 kJ/mol, ∑ΔHf,react∘\sum \Delta H^{\circ}_{f,\text{react}} = -74.6 kJ/mol; find ΔHrxn∘\Delta H^{\circ}_{\text{rxn}} (standard enthalpy of reaction). Methane combustion: -965.1 - (-74.6) → -890.5 kJ/mol.

Module 1 practice

1. Heat in the cup: A calorimetry class heats 200 g of water in an open cup from 18.0 °C to 43.0 °C. Take the specific heat capacity of water as 4.18 J/(g·°C). Calculate the heat absorbed by the water.

2. Heat in the cup: A 250 g portion of hot water is left in a coffee-cup calorimeter and cools from 72.0 °C to 62.0 °C. Take the specific heat capacity of water as 4.18 J/(g·°C). Calculate the heat change of the water, sign included.

3. Warming and melting: A 20 g block of ice sits at 0 °C in an insulated flask. Heat is supplied until the last of it has just melted, with the mixture still at 0 °C. For water, the latent heat of fusion is 334 J/g and the latent heat of vaporization is 2260 J/g. Calculate the heat required to melt the ice.

4. Warming and melting: On the same heating curve, 250 g of liquid water is warmed by 10 C° along the slope between the two plateaus. Take c = 4.18 J/(g·°C); for water the latent heat of fusion is 334 J/g. Calculate the heat absorbed along that slope.

5. Heat per mole: A 64.0 g sample of methanol (CH₃OH, M = 32.0 g/mol) is burned completely. Its molar enthalpy of combustion is -726 kJ/mol. Calculate the heat change for the sample, sign included.

6. Heat per mole: A 92.0 g sample of ethanol (C₂H₅OH, M = 46.0 g/mol) is burned completely. Its molar enthalpy of combustion is -1367 kJ/mol. Calculate the heat change for the sample, sign included.

7. The coffee cup: In a coffee-cup calorimeter, 50.0 mL of 1.00 mol/L hydrochloric acid is mixed with 50.0 mL of 1.00 mol/L sodium hydroxide, both starting at the same temperature. The mixture warms by 7.2 C°. Treat the combined solution as 100 g of water with c = 4.18 J/(g·°C), and assume the calorimeter itself absorbs no heat. Determine the molar enthalpy of neutralization, per mole of acid.

8. The coffee cup: In a coffee-cup calorimeter, 200.0 mL of 0.50 mol/L copper(II) sulfate solution is stirred with an excess of zinc powder. The solution warms by 24.0 C°. Treat the solution as 200 g of water with c = 4.18 J/(g·°C), and assume the calorimeter itself absorbs no heat. Determine the molar enthalpy of reaction, per mole of copper(II) ion.

9. The ladder of Hess: A data sheet gives three reactions bearing on the formation of ethene. Step 1: C(s) + O₂(g) → CO₂(g), ΔH = -394 kJ/mol. Step 2: H₂(g) + ½ O₂(g) → H₂O(l), ΔH = -286 kJ/mol. Step 3: C₂H₄(g) + 3 O₂(g) → 2 CO₂(g) + 2 H₂O(l), ΔH = -1411 kJ/mol. The target reaction is 2 C(s) + 2 H₂(g) → C₂H₄(g). Each step may be reversed, or multiplied through, before the sum is taken. Determine the enthalpy change of the target reaction.

10. The ladder of Hess: A data sheet gives three reactions bearing on the formation of acetylene. Step 1: C(s) + O₂(g) → CO₂(g), ΔH = -394 kJ/mol. Step 2: H₂(g) + ½ O₂(g) → H₂O(l), ΔH = -286 kJ/mol. Step 3: C₂H₂(g) + 5/2 O₂(g) → 2 CO₂(g) + H₂O(l), ΔH = -1300 kJ/mol. The target reaction is 2 C(s) + H₂(g) → C₂H₂(g). Each step may be reversed, or multiplied through, before the sum is taken. Determine the enthalpy change of the target reaction.

11. The formation shortcut: A standard thermochemistry table is used to evaluate the balanced reaction CaCO₃(s) → CaO(s) + CO₂(g). The table lists ΔH°f(CaO(s)) = -635 kJ/mol; ΔH°f(CO₂(g)) = -394 kJ/mol; ΔH°f(CaCO₃(s)) = -1207 kJ/mol. All values are quoted at 25 °C and 100 kPa. Determine the standard enthalpy change of the reaction.

12. The formation shortcut: A standard thermochemistry table is used to evaluate the balanced reaction 2 SO₂(g) + O₂(g) → 2 SO₃(g). The table lists ΔH°f(SO₃(g)) = -396 kJ/mol; ΔH°f(SO₂(g)) = -297 kJ/mol. It prints no entry at all for an element in its standard state. All values are quoted at 25 °C and 100 kPa. Determine the standard enthalpy change of the reaction.

13. The Heat Audit: End of shift in the calibration lab. A 5.0 g pellet of fuel X (M = 20.0 g/mol) is burned completely in a calorimeter holding 500 g of water. The molar enthalpy of combustion of X is −210 kJ/mol, all of the heat reaches the water, and today c = 4.2 J/(g·°C) because the calculator is locked in the drawer. The protocol only signs off on the run if the water's temperature rise reaches at least 30 C°. Work each line — every answer feeds the next. Determine whether this run meets the protocol's temperature-rise specification.

14. The Heat Audit: Bonus mark, no calculator. A route to a target reaction runs through three tabulated steps: ΔH₁ = -400 kJ/mol, ΔH₂ = -300 kJ/mol, ΔH₃ = -1600 kJ/mol. Step 1 must be doubled, step 2 must be doubled, and step 3 must be reversed. Determine the enthalpy change of the target reaction.

Module 2

Rates & Kinetics

Reading the rate law · Arrhenius and the hill · Two temperatures · Straight-line decay · The half-life clock · Second-order slowdown · The Rate Tribunal

In BC Chemistry 12 · Ontario SCH4U

(Chemistry 12-9)r=k CA nr = k\,C_A^{\,n}
Where
  • rr= Reaction rate (mol/(m³·s))
  • kk= Rate constant ((mol/m³)^(1−n)·s⁻¹)
  • CAC_A= Concentration of A (M)
  • nn= Reaction order
ln rln CA1nln k
Figure 2.1: power-law reaction rate.

The power-law rate expression, r=kCA nr = k C_A^{\,n}, is an empirical fit rather than a law of nature, and treating it as more than that causes most of the trouble it gets into. The order nn is a number found by measuring rates at different concentrations and fitting a straight line to ln⁡r\ln r against ln⁡CA\ln C_A. It is NOT read off the balanced equation. Only an elementary reaction, one that really does happen in a single molecular collision, has orders equal to its stoichiometric coefficients, and most industrially interesting reactions are multi-step sequences that do not.

Fractional orders are therefore ordinary rather than pathological. An order of 1.5 usually signals a chain mechanism; an order of 0.5 often means a dimer dissociating before the rate-determining step; an order that starts near 1 at low concentration and falls toward 0 at high is the signature of a catalyst surface saturating, which the Langmuir–Hinshelwood form describes properly. A NEGATIVE order is real too, and means a species inhibits its own reaction: typically a product competing for the same active sites.

Now the part this site cannot fix for you, and the reason this page carries a warning the others do not. The units of kk depend on nn. At first order kk is s⁻¹. At second order it is m³/(mol·s). At an order of 1.5 it is (mol/m³)−0.5·s⁻¹, which has no name and no entry in any unit converter, because its dimensions are not known until the reader supplies nn. This calculator therefore takes kk as a plain SI number and converts nothing: whatever you type is used exactly as typed.

That makes one specific error very easy and very expensive. Kinetics tables almost universally publish second-order constants in L/(mol·s), and SI wants m³/(mol·s): a factor of 1000. Third-order constants are out by a million. The concentration boxes on this page do convert, so entering 2 mol/L correctly becomes 2000 mol/m³ internally; the kk box cannot. Divide a tabulated second-order constant by 1000 before it goes in, and check the resulting rate against something you know (a half-life, a conversion you have measured) before it sizes a vessel. A silent factor of a thousand in a reactor volume is not a rounding error.

Worked example 2.1. Given kk = 0.01, CAC_A = 2.0 M, nn = 1; find rr (reaction rate). First order, k = 0.01 s⁻¹ at 2.00 M → r = 20.0 mol/(m³·s).

(Chemistry 12-10)k=A e−Ea/RTk = A\,e^{-E_a/RT}
Where
  • kk= Rate constant (Hz)
  • AA= Pre-exponential factor (Hz)
  • EaE_a= Activation energy (kJ/mol)
  • TT= Absolute temperature (°C)
EakAT
Figure 2.2: arrhenius equation.

Molecules collide constantly, but only the small fraction carrying enough energy to climb the activation barrier actually react. The Boltzmann factor e−Ea/RTe^{-E_a/RT} is that fraction, and A is roughly the collision frequency with the right geometry, so the rate constant is "how often they meet" times "how often the meeting is violent enough". Because EaE_a sits in an exponent, the temperature dependence is ferocious: for a typical EaE_a near 50 kJ/mol, a 10 K rise around room temperature roughly doubles the rate, the old rule of thumb behind refrigerating food and running reactions under reflux.

Svante Arrhenius proposed the form in 1889 after Jacobus van 't Hoff's thermodynamic argument suggested it. He was no stranger to sceptical committees: his 1884 Uppsala doctoral thesis on electrolytic dissociation, the claim that salts split into ions in water, so baffled his examiners that they awarded it the lowest passing grade, nearly ending his career. Nineteen years later the same work won him the 1903 Nobel Prize in Chemistry. A worked case: a reaction with A = 1.0 × 10¹³ s⁻¹ whose rate constant is 1.0 × 10⁻³ s⁻¹ at 300 K has EaE_a = RT ln(A/k) = 8.314 × 300 × ln(10¹⁶) = 91.9 kJ/mol. Only the ratio A/k matters here, so any consistent pair of rate-constant units works.

Worked example 2.2. Given kk = 1.0e-3 Hz, AA = 1.0e13 Hz, TT = 300 K; find EaE_a (activation energy). A = 1e13 /s, k = 1e-3 /s at 300 K → Ea = 91.895 kJ/mol.

(Chemistry 12-11)ln⁡k2k1=EaR(1T1−1T2)\ln\frac{k_2}{k_1} = \frac{E_a}{R}\left(\frac{1}{T_1} - \frac{1}{T_2}\right)
Where
  • k1k_1= Rate constant at T1 (Hz)
  • k2k_2= Rate constant at T2 (Hz)
  • EaE_a= Activation energy (kJ/mol)
  • T1T_1= First absolute temperature (°C)
  • T2T_2= Second absolute temperature (°C)
T1T2k1k2Ea
Figure 2.3: arrhenius two-temperature form.

Write the Arrhenius equation twice, once at each temperature, and divide: the pre-exponential factor A cancels and only the ratio of rate constants survives. That is a gift to the experimentalist, because A is hard to measure but a rate ratio needs only two runs on the same apparatus. Since only k₂/k₁ appears, the units of the rate constants are irrelevant as long as both are the same: half-lives work just as well, inverted.

The classic result: a reaction whose rate exactly doubles between 300 K and 310 K has EaE_a = R ln 2 / (1/300 − 1/310) = 8.314 × 0.693 × 9300 = 53.6 kJ/mol. That is where the "rates double every 10 degrees" rule of thumb comes from: it is only true for activation energies near 50 kJ/mol, and it fails badly for very fast or very slow reactions. The two traps are using Celsius instead of kelvin (this calculator converts for you, but a hand calculation will be wildly wrong) and reversing the reciprocal difference, which flips the sign and hands you a negative activation energy.

Worked example 2.3. Given k1k_1 = 1.00 Hz, k2k_2 = 2.00 Hz, T1T_1 = 300 K, T2T_2 = 310 K; find EaE_a (activation energy). Rate doubles 300 K → 310 K: Ea = 53.597 kJ/mol.

(Chemistry 12-12)Ea=−R×slopeE_a = -R \times \text{slope}
Where
  • EaE_a= Activation energy (kJ/mol)
  • slope\text{slope}= Slope of ln k vs 1/T, in kelvin (K)
slopeEa
Figure 2.4: activation energy from an arrhenius plot.

Take logarithms of the Arrhenius equation and it straightens out: ln k = ln A − (Ea/R)(1/T)(E_a/R)(1/T). Plot ln k on the vertical axis against 1/T on the horizontal and you get a line whose slope is −Ea/R-E_a/R and whose intercept is ln A. Multiplying the slope by −R (8.314 J/(mol·K)) recovers the activation energy from as many data points as you care to collect, which is far more robust than the two-point method because random scatter averages out across the whole set.

A measured slope of −6448 K gives EaE_a = 8.314 × 6448 = 53.6 kJ/mol, the same value a doubling-per-10-K experiment would yield. The slope has units of kelvin, and it is always negative for a normal reaction: a positive slope means the reaction speeds up on cooling, which happens only in unusual multi-step systems with a negative apparent activation energy. Watch the axis scaling too: 1/T values cluster in a narrow band (1/300 to 1/320 spans only 0.00021), so plotting the reciprocal to too few decimal places wrecks the slope long before the chemistry does.

Worked example 2.4. Given slope\text{slope} = -6447.7; find EaE_a (activation energy). Arrhenius slope -6447.7 K → Ea = 53.609 kJ/mol.

(Chemistry 12-13)[A]=[A]0−kt[\mathrm{A}] = [\mathrm{A}]_0 - kt
Where
  • [A][\mathrm{A}]= Concentration at time t (M)
  • [A]0[\mathrm{A}]_0= Initial concentration (M)
  • kk= Rate constant in mol/(L·s) (mol/(L·s))
  • tt= Elapsed time (s)
[A]0t[A]k
Figure 2.5: zero-order integrated rate law.

A zero-order reaction consumes reactant at a fixed rate no matter how much is left, so a plot of concentration against time is a straight line of slope −k. This looks strange until you see the mechanism: it happens when something other than the reactant is the bottleneck (a saturated enzyme, a fully covered catalyst surface, or a photochemical step limited by the lamp). Start at 0.500 M with k = 0.0100 mol/(L·s) and after 20 s exactly 0.200 M has gone, leaving 0.300 M.

Ethanol metabolism is the everyday example: alcohol dehydrogenase saturates at very low blood alcohol levels, so the liver clears roughly 0.015% blood alcohol per hour regardless of how much you drank, which is why "one drink per hour" advice works and why doubling the dose doubles the sobering-up time rather than leaving it unchanged. The unique feature of zero order is that it genuinely runs out: set [A] = 0 and the reaction stops dead at t = [A]₀/k, unlike first-order decay which merely approaches zero forever. Note that k here carries units of mol/(L·s), not the s⁻¹ of a first-order constant.

Worked example 2.5. Given [A]0[\mathrm{A}]_0 = 0.500 M, kk = 0.0100, tt = 20.0 s; find [A][\mathrm{A}] (concentration at time t). 0.500 M zero-order, k = 0.0100 mol/(L·s), 20.0 s → 0.300 M.

(Chemistry 12-14)[A]=[A]0 e−kt[\mathrm{A}] = [\mathrm{A}]_0\,e^{-kt}
Where
  • [A][\mathrm{A}]= Concentration at time t (M)
  • [A]0[\mathrm{A}]_0= Initial concentration (M)
  • kk= First-order rate constant (Hz)
  • tt= Elapsed time (s)
[A]0t[A]k
Figure 2.6: first-order integrated rate law.

In a first-order reaction each molecule decomposes independently with a fixed probability per second, so the rate is proportional to how much is left and the concentration falls exponentially. Taking logarithms gives ln[A] = ln[A]₀ − kt, a straight line: the diagnostic test that distinguishes first order from every other order. The defining property is a constant half-life, t½ = ln2/k = 0.693/k, independent of where you start.

The maths is identical to radioactive decay, which is why the same equation covers the elimination of most drugs from the bloodstream, the fading of a chemiluminescent glow stick, and the isomerisation of cyclopropane to propene. Worked case: with k = 0.0231 s⁻¹, a 0.100 M solution falls to 0.100 × e−0.0231×30e^{-0.0231 \times 30} = 0.0500 M in 30 s, the half-life, since 0.693/0.0231 = 30.0 s. The usual arithmetic slip is mixing k in s⁻¹ with a time in minutes; the calculator converts both to SI first, so enter each with its real unit rather than pre-converting.

Worked example 2.6. Given [A]0[\mathrm{A}]_0 = 0.100 M, kk = 0.0231 Hz, tt = 30.0 s; find [A][\mathrm{A}] (concentration at time t). 0.100 M first-order, k = 0.0231 /s, 30.0 s → 0.0500074 M.

(Chemistry 12-15)N=N0(12)t/t1/2N = N_0 \left(\frac{1}{2}\right)^{t/t_{1/2}}
Where
  • NN= Remaining quantity
  • N0N_0= Initial quantity
  • tt= Elapsed time (s)
  • t1/2t_{1/2}= Half-life (s)
N0t1/2tN
Figure 2.7: half-life decay.

Radioactive decay never runs out of sample all at once: it halves, and halves again, forever. Each half-life leaves exactly 50% of what entered it, so after two half-lives a quarter remains, after ten about a thousandth. Carbon-14, with its 5,730-year half-life, is the famous example: a bone whose C-14 content has fallen to one quarter of the living value has been dead roughly 11,460 years. N and N0N_0 can be in any matching unit (grams, atom counts, or becquerels) since only their ratio matters.

Solving for time or half-life inverts the exponential with a base-2 logarithm, which demands 0 < N < N0N_0: you cannot take the log of a zero ratio, and decay never leaves more than it started with. The same mathematics governs drug elimination in pharmacology and the six-hour half-life of technetium-99m, the workhorse isotope of medical imaging.

Worked example 2.7. Given N0N_0 = 100, tt = 11460 yr, t1/2t_{1/2} = 5730 yr; find NN (remaining quantity). C-14: 100 units after 11460 yr (2 half-lives) → 25 remain.

(Chemistry 12-16)t1/2=ln⁡2λt_{1/2} = \frac{\ln 2}{\lambda}
Where
  • t1/2t_{1/2}= Half-life (s)
  • λ\lambda= Decay constant (Hz)
t1/2λ
Figure 2.8: half-life and decay constant.

Half-life and decay constant are the same fact in two dialects. The decay constant λ is the fundamental one: it is the probability per unit time that any individual nucleus, chosen at random and regardless of its history, will decay. That single assumption, a constant per-nucleus probability, produces the exponential law N=N0e−λtN = N_0 e^{-\lambda t} and nothing else. The half-life is what you get by asking that law when N/N0=12N/N_0 = \tfrac{1}{2}: take logarithms and t1/2=ln⁡2/λt_{1/2} = \ln 2/\lambda, with ln 2 = 0.6931471806. Large λ, short half-life. The two numbers carry identical information, and which one a source quotes is a matter of discipline rather than physics.

Cobalt-60 has a half-life of 5.27 years, so λ=0.6931/5.27=0.1315\lambda = 0.6931/5.27 = 0.1315 per year, or 4.17×10−94.17 \times 10^{-9} per second once the years are converted. That per-second figure is the useful one, because activity is A=λNA = \lambda N. One gram of Co-60 holds 6.022×1023/60=1.00×10226.022\times10^{23}/60 = 1.00\times10^{22} nuclei, so its activity is 4.17×10−9×1.00×1022≈4.2×10134.17\times10^{-9} \times 1.00\times10^{22} \approx 4.2\times10^{13} Bq: about 42 TBq, or 1100 curies, from a single gram. λ is what converts a count of atoms into a radiation hazard.

A third quantity lives in the same family and is the one most often mixed up with the others. The mean lifetime τ, the average time an individual nucleus survives before decaying, is simply 1/λ1/\lambda, which makes it t1/2/ln⁡2=1.443 t1/2t_{1/2}/\ln 2 = 1.443\,t_{1/2}. The mean life is 44% longer than the half-life, and they are not interchangeable. Particle physics tables usually quote τ, nuclear medicine and health physics usually quote t1/2t_{1/2}, and a value copied across that boundary without conversion is wrong by a factor you will not notice from the magnitude alone. The same structure appears wherever a fixed fractional loss per unit time does: drug clearance, capacitor discharge through a resistor, the attenuation of light through an absorbing medium.

The unit trap is mechanical and unforgiving: λ and t1/2t_{1/2} are reciprocals, so their units must be reciprocals too. A λ quoted per year set against a time measured in seconds is off by 3.16×1073.16\times10^7. Decide on one time unit at the start and hold it through the whole problem.

One property of λ is worth stating because it is genuinely unusual. It does not depend on temperature, on pressure, on the chemical compound the atom sits in, or on how long the nucleus has already existed. Essentially every chemical rate constant doubles or better for a 10 K rise; λ does not move. Heating a radioactive sample, dissolving it, or bonding it into a molecule changes nothing measurable, because the decay is a nuclear event and chemistry happens far outside the nucleus. In living systems, though, a second clock runs alongside: a radiopharmaceutical is also excreted, and the two combine as 1/Teff=1/Tphys+1/Tbio1/T_{eff} = 1/T_{phys} + 1/T_{bio}, so the effective half-life in a patient is always shorter than the physical one.

Worked example 2.8. Given t1/2t_{1/2} = 138.4 d; find λ\lambda (decay constant). Po-210: t_half = 138.4 d → lambda = 5.79663e-8 /s.

(Chemistry 12-17)1[A]=1[A]0+kt\frac{1}{[\mathrm{A}]} = \frac{1}{[\mathrm{A}]_0} + kt
Where
  • [A][\mathrm{A}]= Concentration at time t (M)
  • [A]0[\mathrm{A}]_0= Initial concentration (M)
  • kk= Rate constant in L/(mol·s) (L/(mol·s))
  • tt= Elapsed time (s)
[A]0t[A]k
Figure 2.9: second-order integrated rate law.

When two molecules of the same reactant must find each other, the rate goes as [A]², and integrating gives a straight line only if you plot the reciprocal concentration against time. The slope of that line is k, in L/(mol·s). Starting at 0.100 M with k = 0.500 L/(mol·s), after 10 s the reciprocal has climbed from 10 to 10 + 5 = 15, so [A] = 0.0667 M.

The three integrated laws form the standard diagnostic kit: plot [A] versus t, ln[A] versus t, and 1/[A] versus t, and whichever comes out straight tells you the order. Second-order kinetics has a distinctive personality: it starts fast and then drags, because losing reactant hurts the rate twice over. Gas-phase NO₂ decomposition and many radical recombinations follow it. Be careful with the "pseudo" cases: a reaction that is genuinely second order overall but run with a huge excess of one partner behaves like first order in the other, which is exactly how kineticists tame a two-variable problem into a one-variable measurement.

Worked example 2.9. Given [A]0[\mathrm{A}]_0 = 0.100 M, kk = 0.500, tt = 10.0 s; find [A][\mathrm{A}] (concentration at time t). 0.100 M second-order, k = 0.500 L/(mol·s), 10.0 s → 0.0666667 M.

(Chemistry 12-18)t1/2=1k [A]0t_{1/2} = \frac{1}{k\,[\mathrm{A}]_0}
Where
  • t1/2t_{1/2}= Half-life (s)
  • kk= Rate constant in L/(mol·s) (L/(mol·s))
  • [A]0[\mathrm{A}]_0= Initial concentration (M)
[A]0t1/2k
Figure 2.10: half-life of a second-order reaction.

Set [A] = [A]₀/2 in the second-order integrated law and the reciprocals collapse to t½ = 1/(k[A]₀). The consequence is counterintuitive if you are used to radioactive decay: the half-life is not a constant of the reaction but depends on where you start, and it doubles every time you halve the concentration. With k = 0.200 L/(mol·s) and [A]₀ = 0.500 M the first half-life is 1/(0.200 × 0.500) = 10.0 s; the next half, from 0.250 M down to 0.125 M, takes 20.0 s, then 40.0 s, and so on.

That lengthening tail is the signature of second-order kinetics and a genuinely useful diagnostic at the bench: measure successive half-lives and if they keep doubling, the reaction is second order; if they stay constant, first order; if they keep halving, zero order. It also explains why the last traces of a dimerising impurity are so stubborn to remove: the reaction that cleans it up slows down quadratically as the impurity thins out.

Worked example 2.10. Given kk = 0.200, [A]0[\mathrm{A}]_0 = 0.500 M; find t1/2t_{1/2} (half-life). k = 0.200 L/(mol·s), 0.500 M → t_half = 10.0 s.

Module 2 practice

15. Arrhenius and the hill: A kinetics table lists a first-order reaction with A = 1.0 × 10¹⁴ s⁻¹ and Ea = 80.0 kJ/mol. A technician runs it in a thermostatted bath at 127 °C. Calculate the rate constant at that temperature.

16. Arrhenius and the hill: A kinetics table lists a first-order reaction with A = 1.0 × 10¹⁴ s⁻¹ and Ea = 80.0 kJ/mol. A technician runs it in a thermostatted bath at 127 °C. Calculate the rate constant at that temperature.

17. Two temperatures: The same reaction is timed twice. At 27 °C its rate constant is 2.0 × 10⁻³ s⁻¹; at 37 °C the same reaction returns 4.0 × 10⁻³ s⁻¹. Subscript 1 is the cooler run, subscript 2 the warmer one. Determine the activation energy of the reaction, in kJ/mol.

18. Two temperatures: A class measures the rate constant of one reaction at five temperatures, plots ln k against 1/T, and finds the points fall on a straight line of slope −5.00 × 10³ K. Calculate the activation energy from the slope, in kJ/mol.

19. Straight-line decay: A decomposition running on a fully saturated catalyst surface — every site busy, so the rate never changes — a zero-order reaction. It starts at 1.20 mol/L with a rate constant of 0.0100 mol/(L·s), and runs undisturbed for 30.0 s. Calculate the concentration of reactant remaining.

20. Straight-line decay: A dissolved drug clears the bloodstream by a first-order route, with a rate constant of 0.0462 s⁻¹. The sample begins at 0.800 mol/L and is left for 30.0 s. Determine the concentration remaining at that time.

21. The half-life clock: A radiolabelled compound in a shielded vial decays by a first-order process with a rate constant of 0.0578 s⁻¹. Calculate the half-life of the sample.

22. The half-life clock: An isotope tracer in a hospital's hot lab is observed to lose exactly half of its reactant every 10.0 s. Determine the first-order rate constant.

23. Second-order slowdown: Two NO₂ molecules must meet for this decomposition to happen at all, which makes it second order. It begins at 0.100 mol/L with a rate constant of 0.150 L/(mol·s), and is followed for 100 s. Calculate the concentration remaining.

24. Second-order slowdown: A second-order dimerization has a rate constant of 0.500 L/(mol·s). A run is charged at 0.0400 mol/L. Determine the half-life of this run.

25. The Rate Tribunal: The last batch of the shift. A reactant decomposes by a first-order route. At 300 K the plant logs an initial rate of 0.050 mol/(L·s) with the tank charged at 5.0 mol/L. The operator then warms the tank to 310 K — ten degrees, and this reaction is one of the well-behaved ones whose rate constant DOUBLES over that step — and holds it there for 105 s. Plant rules: the batch may be discharged only once less than 10 % of the original reactant is left. No calculator, and today ln 2 = 0.70. Work each line — every answer feeds the next. Determine whether this batch may be discharged, one line at a time.

26. The Rate Tribunal: Bonus mark, still no calculator. On a separate bench trial the technician doubles the concentration of A, holds the temperature, and watches the initial rate rise by a factor of 4. Determine the order in A, then predict what tripling the concentration would do.

Module 3

Chemical Equilibrium

Writing K · Q against K · Kp meets Kc · Sparingly soluble · Gibbs decides · The Position of Equilibrium

In BC Chemistry 12 · Alberta Chemistry 30 · Ontario SCH4U

3.1 Equilibrium Constant Kc (A + B ⇌ C + D)

Solve it online →formula.expert/solvers/equilibrium-constant-kc
(Chemistry 12-19)Kc=[C][D][A][B]K_c = \frac{[\mathrm{C}][\mathrm{D}]}{[\mathrm{A}][\mathrm{B}]}
Where
  • KcK_c= Equilibrium constant (or quotient Q)
  • [C][\mathrm{C}]= Concentration of product C (M)
  • [D][\mathrm{D}]= Concentration of product D (M)
  • [A][\mathrm{A}]= Concentration of reactant A (M)
  • [B][\mathrm{B}]= Concentration of reactant B (M)
[A][B][C][D]Kc
Figure 3.1: equilibrium constant kc (a + b ⇌ c + d).

Cato Guldberg and Peter Waage, two brothers-in-law working in Kristiania (now Oslo), published the law of mass action in 1864: at equilibrium the products of the concentrations, each raised to its stoichiometric coefficient, sit in a fixed ratio. For the common one-to-one case A + B ⇌ C + D that ratio is just [C][D]/([A][B]). Their paper appeared in Norwegian and was ignored for a decade until a French translation reached van 't Hoff and Ostwald.

The identical expression evaluated with any set of concentrations, not necessarily equilibrium ones, is the reaction quotient Q, and comparing Q with Kc predicts which way the reaction will run: Q < Kc means it goes forward, Q > Kc means it reverses, Q = Kc means it is already there. Worked example: with [C] = [D] = 0.60 M and [A] = 0.20 M, [B] = 0.30 M, the quotient is 0.36/0.060 = 6.0, so if Kc were 2.0 the mixture would run backwards to consume product. Note that this calculator assumes all four coefficients are 1; with other coefficients each concentration needs its own exponent.

Worked example 3.1. Given [C][\mathrm{C}] = 0.60 M, [D][\mathrm{D}] = 0.60 M, [A][\mathrm{A}] = 0.20 M, [B][\mathrm{B}] = 0.30 M; find KcK_c (equilibrium constant (or quotient q)). [C]=[D]=0.60 M over [A]=0.20, [B]=0.30 M → Kc = 6.00.

(Chemistry 12-20)Q=[C]c[A]a [B]bQ = \frac{[\mathrm{C}]^{c}}{[\mathrm{A}]^{a}\,[\mathrm{B}]^{b}}
Where
  • QQ= Reaction quotient
  • [A][\mathrm{A}]= Concentration of reactant A (M)
  • aa= Coefficient of reactant A
  • [B][\mathrm{B}]= Concentration of reactant B (M)
  • bb= Coefficient of reactant B
  • [C][\mathrm{C}]= Concentration of product C (M)
  • cc= Coefficient of product C
a[A]b[B]c[C]Q
Figure 3.2: reaction quotient q (aa + bb ⇌ cc).

Q is built from exactly the same expression as the equilibrium constant (products over reactants, each raised to its balanced coefficient) but you are allowed to evaluate it with any concentrations, not just equilibrium ones. That is the whole point. Q is a snapshot of where a mixture currently stands; K is where it is heading. Compare them and you have the direction of shift for free: Q < K means too much reactant, so the reaction runs forward; Q > K means too much product, so it reverses; Q = K means the mixture is already at equilibrium and nothing net happens.

Each concentration is divided by the standard state c° = 1 mol/L before it is raised to its power, which is what makes Q a pure number even when the powers do not balance. This page covers the very common aA + bB ⇌ cC shape; for a reaction with two products and matching one-to-one coefficients, use the Kc calculator instead. A species that does not appear on the reactant side can be switched off by entering a coefficient of 0: pure solids and pure liquids are always left out, which is why the water in an aqueous equilibrium never shows up.

Henry Le Chatelier, whose 1884 principle is the qualitative version of this comparison, paid dearly for not having the quantitative one. He ran nitrogen and hydrogen together at high pressure looking for ammonia, an explosion in his laboratory nearly killed an assistant, and he abandoned the work: later calling it "the greatest blunder of my scientific career". The explosion was caused by air left in the apparatus, not by the equilibrium. Fritz Haber took it up two decades later. Worked case, on Le Chatelier's own reaction N₂ + 3H₂ ⇌ 2NH₃: with [N₂] = 0.50 M, [H₂] = 0.20 M and [NH₃] = 0.10 M, Q = (0.10)²/[(0.50)(0.20)³] = 0.010/0.0040 = 2.5. If K at that temperature is 0.060, then Q > K and the mixture will run backwards, decomposing ammonia: the difference between a plant that makes fertiliser and one that does not.

Worked example 3.2. Given [A][\mathrm{A}] = 0.50 M, aa = 1, [B][\mathrm{B}] = 0.20 M, bb = 3, [C][\mathrm{C}] = 0.10 M, cc = 2; find QQ (reaction quotient). Haber snapshot 0.50/0.20/0.10 M → Q = 2.5.

(Chemistry 12-21)Kp=Kc(RT)ΔnK_p = K_c (RT)^{\Delta n}
Where
  • KpK_p= Pressure equilibrium constant
  • KcK_c= Concentration equilibrium constant
  • Δn\Delta n= Change in moles of gas
  • TT= Absolute temperature (°C)
KpΔnKcT
Figure 3.3: kp from kc (kp = kc(rt)^δn).

Gas-phase equilibria can be written with partial pressures or with molar concentrations, and the ideal gas law (P = (n/V)RT) converts between them one species at a time. Every mole of gas on the product side contributes a factor of RT and every mole on the reactant side removes one, so only the net change Δn survives: Kp = Kc(RT)Δn(RT)^{\Delta n}. This calculator uses R = 0.08206 L·atm/(mol·K), the value that pairs partial pressures in atmospheres with concentrations in mol/L.

Δn counts gases only: solids and liquids never appear in either constant. For the Haber synthesis N₂ + 3H₂ ⇌ 2NH₃, Δn = 2 − 4 = −2, so Kp is far smaller than Kc at high temperature. Where Δn = 0, as in H₂ + I₂ ⇌ 2HI, the two constants are numerically identical and the whole conversion evaporates. A worked case: a reaction with Δn = +1 and Kc = 1.00 at 1000 K has Kp = 1.00 × (0.08206 × 1000) = 82.1, a reminder that "the" equilibrium constant is meaningless until you say which basis you meant.

Worked example 3.3. Given KcK_c = 1.000, Δn\Delta n = 1, TT = 1000 K; find KpK_p (pressure equilibrium constant). Kc = 1.000, dn = +1 at 1000 K → Kp = 82.0574.

(Chemistry 12-22)PV=nRTP V = n R T
Where
  • PP= Pressure (kPa)
  • VV= Volume (L)
  • nn= Amount (mol)
  • TT= Temperature (°C)
PVTn
Figure 3.4: ideal gas law.

PV=nRTPV = nRT says that for a gas, four quantities are not independent: fix any three and the fourth is decided. Squeeze it and the pressure rises; warm it and it pushes harder or swells; add more of it and both go up. What makes the equation remarkable is not that those things are true, anyone with a bicycle pump knows them, but that one constant serves every gas. Helium, nitrogen and steam all obey it with the same R=8.314R = 8.314 J/(mol·K), which is a strong hint that pressure has nothing to do with what the molecules are and everything to do with how many there are and how fast they are moving.

A worked case in units you would actually read off a gauge. A 20 L cylinder sits at 150 kPa absolute on a 20 °C morning. Rearranged for amount, n=PV/RT=(150 000×0.020)/(8.314×293.15)=3000/2437≈1.23 moln = PV/RT = (150\,000 \times 0.020)/(8.314 \times 293.15) = 3000/2437 \approx 1.23\ \text{mol}. Note what had to happen before the arithmetic: pascals not kilopascals, cubic metres not litres, and kelvin not Celsius. This page converts your entries for you, but the discipline is worth keeping in your head, because a scrap of paper will not.

The law arrived in pieces. Boyle established PVPV constant at fixed temperature in 1662; Charles and Gay-Lussac tied volume and pressure to temperature around 1800; Avogadro proposed in 1811 that equal volumes of gases hold equal numbers of particles. Émile Clapeyron folded them into a single expression in 1834. Kinetic theory later derived the whole thing from mechanics: treat molecules as point masses that bounce elastically and never attract one another, average over their collisions with the walls, and PV=nRTPV = nRT falls out, with RTRT revealed as a measure of the average kinetic energy per mole.

Those two assumptions are also the fine print, and here a common textbook line deserves correcting. The ideal gas law is a limit, not a fact about gases. Real molecules do occupy volume and do attract each other, so the equation is exact only as pressure approaches zero and the gas gets out of its own way. Near condensation it fails plainly: at 100 atm, or anywhere close to the boiling point, the error runs to tens of percent and you want van der Waals or a compressibility factor. Under ordinary room conditions the error is well under 1%, which is why the approximation earns its keep.

Two errors account for most wrong answers on this page, and both are unit errors rather than physics errors. The first is feeding in Celsius. Doubling a gas from 20 °C to 40 °C does not double anything: in kelvin that is 293 to 313, a rise of 7%, and a calculation that used 20 and 40 would be wrong by a factor of nearly two. The second is feeding in a gauge pressure. A tire gauge reading 220 kPa means 321 kPa absolute; PP here is absolute pressure, measured from vacuum, because the equation counts molecular impacts and vacuum is where there are none. A third, quieter trap: the familiar 22.4 L per mole belongs to 0 °C and 1 atm. IUPAC redefined standard pressure to 100 kPa in 1982, and at that pressure the molar volume is 22.71 L. Both numbers circulate, and quoting one against the other's conditions is a 1.3% error hiding inside a memorised constant.

Worked example 3.4. Given PP = 1 atm, nn = 1 mol, TT = 273.15 K; find VV (volume). 1 mol at 0 C and 1 atm → 22.414 L (molar volume at STP).

(Chemistry 12-23)Ksp=s2K_{sp} = s^{2}
Where
  • KspK_{sp}= Solubility product ((mol/L)²)
  • ss= Molar solubility (M)
sKsp
Figure 3.5: solubility product of a 1:1 salt.

Drop silver chloride into water and a little dissolves until the solution is saturated: AgCl(s) ⇌ Ag⁺ + Cl⁻. The solid's concentration never appears in an equilibrium expression, so Ksp is simply [Ag⁺][Cl⁻], and because each formula unit hands over one of each ion, both equal the molar solubility s. Hence Ksp = s². AgCl dissolves to about 1.3 × 10⁻⁵ M, giving Ksp = 1.7 × 10⁻¹⁰: a number small enough that gravimetric chloride analysis can assume essentially all the silver precipitates.

Running it backwards is just as useful: barium sulfate's Ksp of 1.1 × 10⁻¹⁰ gives s = √(1.1 × 10⁻¹⁰) = 1.05 × 10⁻⁵ M, which is why patients can safely swallow a barium meal of a compound whose free Ba²⁺ ion is highly toxic. Almost none of it ever enters solution. The trap is the common-ion effect: this s = √Ksp shortcut assumes pure water. Add 0.10 M NaCl and AgCl's solubility collapses to Ksp/[Cl⁻] ≈ 1.7 × 10⁻⁹ M, a hundredfold drop, which is exactly how analysts force a precipitation to completion.

Worked example 3.5. Given ss = 0.013 mM; find KspK_{sp} (solubility product). AgCl s = 1.3e-5 M (0.013 mM) → Ksp = 1.69e-10.

(Chemistry 12-24)Ksp=4s3K_{sp} = 4s^{3}
Where
  • KspK_{sp}= Solubility product ((mol/L)³)
  • ss= Molar solubility (M)
sKsp
Figure 3.6: solubility product of an ab₂ salt.

When a salt dissolves into three ions instead of two the arithmetic changes shape. CaF₂(s) ⇌ Ca²⁺ + 2F⁻ releases one calcium and two fluorides per formula unit, so if s moles dissolve per litre then [Ca²⁺] = s but [F⁻] = 2s, and Ksp = s(2s)² = 4s³. Calcium fluoride's molar solubility of 2.15 × 10⁻⁴ M therefore gives Ksp = 4(2.15 × 10⁻⁴)³ = 4.0 × 10⁻¹¹, matching the handbook value.

Reversed, Mg(OH)₂ with Ksp = 5.6 × 10⁻¹² dissolves to s = ∛(5.6 × 10⁻¹² / 4) = 1.1 × 10⁻⁴ M: enough hydroxide to buffer a stomach at pH about 10 in the flask, which is the entire pharmacology of milk of magnesia. The universal trap is dropping the 4, or forgetting that the doubled ion gets both a coefficient and an exponent. Also note that Ksp alone does not rank solubility across different stoichiometries: AgCl (Ksp 1.7 × 10⁻¹⁰) is actually less soluble than Mg(OH)₂ despite the larger constant, because the exponents differ.

Worked example 3.6. Given ss = 2.15e-4 M; find KspK_{sp} (solubility product). CaF2 s = 2.15e-4 M → Ksp = 4s³ = 3.97535e-11.

3.7 Gibbs Free Energy Change (ΔG = ΔH − TΔS)

Solve it online →formula.expert/solvers/gibbs-free-energy-change
(Chemistry 12-25)ΔG=ΔH−T ΔS\Delta G = \Delta H - T\,\Delta S
Where
  • ΔG\Delta G= Gibbs free energy change (kJ/mol)
  • ΔH\Delta H= Enthalpy change (kJ/mol)
  • TT= Absolute temperature (°C)
  • ΔS\Delta S= Entropy change (J/(mol·K))
ΔHTΔSΔG
Figure 3.7: gibbs free energy change (δg = δh − tδs).

Josiah Willard Gibbs worked out this balance in "On the Equilibrium of Heterogeneous Substances", published in 1876–78 in the Transactions of the Connecticut Academy of Arts and Sciences: a journal so obscure that European chemists only learned of it after Maxwell began championing the work and Ostwald translated it into German in 1892. The idea is a tug of war: enthalpy pulls a reaction toward lower energy, entropy pulls it toward greater disorder, and temperature decides who wins. ΔG negative means the process can run on its own; ΔG positive means it needs driving; ΔG zero is equilibrium.

Limestone decomposition, CaCO₃ → CaO + CO₂, is the textbook illustration: ΔH = +178.3 kJ/mol (strongly endothermic) and ΔS = +160.5 J/(mol·K) (a gas is released). At 25 °C, ΔG = 178.3 − 298.15 × 0.1605 = +130.4 kJ/mol, so nothing happens. Solve ΔG = 0 for T and you get 178300/160.5 = 1111 K, or about 838 °C, which is why lime kilns are fired to roughly that temperature and no lower. The classic unit trap lives right here: ΔH is tabulated in kJ/mol while ΔS is tabulated in J/(mol·K), and forgetting the factor of 1000 makes the entropy term vanish. Enter ΔS in J/(mol·K) and this calculator handles the rest.

Worked example 3.7. Given ΔH\Delta H = 178.3 kJ/mol, TT = 25 °C, ΔS\Delta S = 160.5 J/(mol·K); find ΔG\Delta G (gibbs free energy change). CaCO3 decomposition at 25 C → dG = +130.447 kJ/mol.

3.8 Gibbs Free Energy and the Equilibrium Constant

Solve it online →formula.expert/solvers/gibbs-equilibrium-constant
(Chemistry 12-26)ΔG∘=−RTln⁡K\Delta G^{\circ} = -RT\ln K
Where
  • ΔG∘\Delta G^{\circ}= Standard free energy change (kJ/mol)
  • KK= Equilibrium constant
  • TT= Absolute temperature (°C)
ΔG°KT
Figure 3.8: gibbs free energy and the equilibrium constant.

Thermodynamic tables and equilibrium tables describe the same chemistry in different currencies, and this equation is the exchange rate. A negative ΔG° means K > 1 and products dominate; a positive ΔG° means K < 1 and reactants win; ΔG° = 0 sits exactly at K = 1. At 25 °C the conversion factor RT is 2.479 kJ/mol, so RT ln 10 = 5.708 kJ/mol: every factor of ten in K is worth 5.7 kJ/mol of free energy. A reaction with K = 1.0 × 10⁵ therefore has ΔG° = −5.708 × 5 = −28.5 kJ/mol.

Because the relationship is exponential, small energy differences produce enormous equilibrium swings: a change of just 11.4 kJ/mol multiplies K by a hundred. That steepness is why enzyme designers and medicinal chemists chase a few kilojoules of binding energy so hard, and why ΔG° values quoted to the nearest kilojoule are already good enough for most predictions. Two cautions: the standard state matters (K must be written with the same reference concentrations and pressures the ΔG° was tabulated for), and this ΔG° is not the ΔG of an actual running mixture. The two differ by RT ln Q, and it is ΔG, not ΔG°, that must reach zero at equilibrium.

Worked example 3.8. Given KK = 1.0e5, TT = 25 °C; find ΔG∘\Delta G^{\circ} (standard free energy change). K = 1.0e5 at 25 C → dG0 = -28.540 kJ/mol.

Module 3 practice

27. Writing K: A sealed vessel holds the one-to-one gas equilibrium A(g) + B(g) ⇌ C(g) + D(g). At equilibrium the concentrations measure [A] = 0.10 M, [B] = 0.20 M, [C] = 0.40 M and [D] = 0.40 M. Determine the equilibrium constant Kc for the reaction as written.

28. Writing K: In an industrial water-gas shift reactor, carbon monoxide and steam settle into equilibrium with carbon dioxide and hydrogen: CO(g) + H₂O(g) ⇌ CO₂(g) + H₂(g). At 700 K the equilibrium concentrations are [CO] = 0.20 M, [H₂O] = 0.20 M, [CO₂] = 0.20 M and [H₂] = 0.60 M. Calculate the equilibrium constant Kc at this temperature.

29. Q against K: At 700 K the water-gas shift CO(g) + H₂O(g) ⇌ CO₂(g) + H₂(g) has Kc = 60. A sample drawn from a running reactor contains [CO] = 0.40 M, [H₂O] = 0.20 M, [CO₂] = 0.80 M and [H₂] = 0.50 M. Calculate the reaction quotient, and state which way the mixture will shift.

30. Q against K: Inside a Haber converter, N₂(g) + 3H₂(g) ⇌ 2NH₃(g) has Kc = 0.060 at the operating temperature. A sample valve is opened mid-run and the mixture reads [N₂] = 0.50 M, [H₂] = 0.20 M and [NH₃] = 0.10 M. Calculate the reaction quotient, and state which way the converter is running.

31. Kp meets Kc: Ammonia is cracked over a hot catalyst to feed a hydrogen line: 2NH₃(g) ⇌ N₂(g) + 3H₂(g). Before Kp and Kc can be compared, the exponent on (RT) has to be settled. Determine Δn for this reaction as written.

32. Kp meets Kc: A sealed tube of colourless dinitrogen tetroxide is warmed until it browns: N₂O₄(g) ⇌ 2NO₂(g). At 300 K the concentration equilibrium constant is Kc = 5.0, and Δn for this reaction is +1. Take R = 0.0821 L·atm/(mol·K). Calculate the pressure equilibrium constant Kp at this temperature.

33. Sparingly soluble: At 25 °C, calcium fluoride (CaF₂) has a solubility product of 3.2 × 10⁻¹¹. Each formula unit releases three ions — two of one, one of the other. Determine the molar solubility of the salt.

34. Sparingly soluble: A saturated solution of magnesium hydroxide (Mg(OH)₂) at 25 °C holds 1.0 × 10⁻⁴ mol/L of dissolved salt. Each formula unit releases three ions — two of one, one of the other. Calculate the solubility product of the salt.

35. Gibbs decides: For the decomposition N₂O₄(g) ⇌ 2NO₂(g), tables give ΔH° = +57 kJ/mol and ΔS° = +176 J/(mol·K). The reaction is run at 298 K. Calculate ΔG° at this temperature, and state whether the reaction is spontaneous.

36. Gibbs decides: For the thermal cracking of a hydrocarbon feed, ΔH° = +150 kJ/mol and ΔS° = +200 J/(mol·K). Both are taken as temperature-independent. Somewhere on the temperature scale ΔG° passes through zero and the reaction changes its mind. Determine the temperature at which ΔG° equals zero.

37. The Position of Equilibrium: Final examination, contact-process unit. In a converter at 300 K, 2SO₂(g) + O₂(g) ⇌ 2SO₃(g) reaches equilibrium with [SO₃] = 0.20 M, [SO₂] = 0.10 M and [O₂] = 0.040 M. A second, freshly charged converter at the same temperature reads [SO₃] = 0.10 M, [SO₂] = 0.20 M and [O₂] = 0.25 M. No calculator: take RT = 25 L·atm/mol, RT = 2500 J/mol, and ln 10 = 2.3. Work each line — every answer feeds the next. Determine whether this equilibrium favours products, working line by line from the concentrations.

38. The Position of Equilibrium: Bonus mark, worked backwards. A second contact-process converter at 300 K is reported only through its thermodynamics: ΔG° = −11.5 kJ/mol for 2SO₂(g) + O₂(g) ⇌ 2SO₃(g). Still no calculator: RT = 2500 J/mol, RT = 25 L·atm/mol, and ln 10 = 2.3. Determine the pressure equilibrium constant for this converter.

Module 4

Acids & Bases

The pH scale · The Kw family · Weak acids and ICE · Buffer country · Dilution discipline · The burette · The Titration Final

In BC Chemistry 12 · Alberta Chemistry 30 · Ontario SCH4U

4.1 pH from Hydrogen Ion Concentration

Solve it online →formula.expert/solvers/ph-hydrogen-ion
(Chemistry 12-27)pH=−log⁡10 [H+]\mathrm{pH} = -\log_{10}\,[\mathrm{H^+}]
Where
  • pH\mathrm{pH}= pH
  • [H+][\mathrm{H^+}]= Hydrogen ion concentration (M)
pH[H+]
Figure 4.1: ph from hydrogen ion concentration.

Hydrogen ion concentrations in water span more than ten orders of magnitude, so in 1909 the Danish chemist Søren Sørensen, working at the Carlsberg brewery laboratory, compressed them onto a logarithmic scale. Each pH unit is a factor of ten: lemon juice at pH 2 carries a hundred times the hydrogen ion concentration of tomato juice at pH 4. Pure water at 25 °C sits at pH 7, where [H⁺] = 1.0 × 10⁻⁷ mol/L. The logarithm takes the concentration in mol/L, and the inverse direction is exact: [H⁺] = 10−pH10^{-\text{pH}}.

In water treatment pH is the master variable. Boiler water is typically held between 10.5 and 11.5 to suppress corrosion, cooling towers near 7–9 to balance scale against corrosion, and municipal drinking water around 7.0–8.5. A pH swing of a single unit, a tenfold chemistry change, is often the first sign that a chemical feed pump has failed.

Worked example 4.1. Given [H+][\mathrm{H^+}] = 0.001 M; find pH\mathrm{pH} (ph). [H+] = 1.0e-3 mol/L → pH = 3.

(Chemistry 12-28)pH+pOH=14\mathrm{pH} + \mathrm{pOH} = 14
Where
  • pH\mathrm{pH}= pH
  • pOH\mathrm{pOH}= pOH
pHpOH
Figure 4.2: ph and poh relation.

Water is never merely water. A small fraction of it is always pulled apart into H⁺ and OH⁻, and the equilibrium between them fixes the product of their concentrations at a constant: Kw=[H+][OH−]=1.0×10−14K_w = [\text{H}^+][\text{OH}^-] = 1.0\times10^{-14} at 25 °C. Because it is a product that is constant, the two concentrations are locked in a see-saw: push one up and the other must come down by the same factor. Take negative logarithms of both sides and the product becomes a sum: pH+pOH=14\mathrm{pH} + \mathrm{pOH} = 14. So pH and pOH are not two independent measurements. They are one number written two ways, and knowing either gives the other for free.

A worked case. Dissolve enough sodium hydroxide to make a 0.010 M solution: it dissociates completely, so [OH−]=1.0×10−2[\text{OH}^-] = 1.0\times10^{-2} and pOH = 2.00. Then pH = 14 − 2.00 = 12.00. Check it the long way, [H+]=Kw/[OH−]=10−14/10−2=10−12[\text{H}^+] = K_w/[\text{OH}^-] = 10^{-14}/10^{-2} = 10^{-12}, giving pH 12.00, and the two routes agree, as they must.

The "14" is not a magic number, it is pKw\mathrm{p}K_w, and the exact value at 25 °C is 13.995. The whole logarithmic apparatus came from Søren Sørensen at the Carlsberg laboratory in 1909, who needed a compact way to talk about hydrogen ion concentrations spanning more than ten orders of magnitude in brewing. The p-prefix now attaches to anything worth compressing that way: pOH, pKa, pKw, pCa.

The trap is that 14 belongs to 25 °C and nothing else. Self-ionisation is endothermic, so heating water drives it forward and KwK_w rises: pKw is about 14.9 at 0 °C, 13.0 at 60 °C, and 12.0 at 100 °C. Which means neutral water at 100 °C has a pH of 6.0, and it is still perfectly neutral, not acidic, because pH still equals pOH. This matters wherever hot water is measured: boiler water sampled at temperature and boiler water sampled after cooling do not read the same, and the difference is the equation moving, not the chemistry changing. Anyone reading pH on a hot sample needs to know whether the meter is compensating and what reference temperature it is compensating to.

Which leads to the deeper misconception. Neutral does not mean pH 7; neutral means pH equals pOH. The two coincide at 25 °C by arithmetic accident, and part company at every other temperature. Two smaller notes: the relation is aqueous only (it says nothing about a non-aqueous solvent, which has its own autoionisation constant if it has one at all) and the pH scale is not fenced between 0 and 14. Those bounds are just where 1 M solutions land. Concentrated hydrochloric acid at 12 M has a negative pH, and concentrated sodium hydroxide runs above 14, with the sum still holding.

Worked example 4.2. Given pH\mathrm{pH} = 4.75; find pOH\mathrm{pOH} (poh). pH 4.75 → pOH = 9.25.

(Chemistry 12-29)Ka Kb=KwK_a \, K_b = K_w
Where
  • KaK_a= Acid dissociation constant
  • KbK_b= Base dissociation constant of the conjugate
  • KwK_w= Ion product of water
KaKbKw
Figure 4.3: ka and kb relation through kw.

Add the dissociation of an acid to the hydrolysis of its conjugate base and the two half-reactions sum to the autoionisation of water, so their equilibrium constants multiply to Kw. That single line means you never need to look up both numbers: acetic acid's Ka of 1.8 × 10⁻⁵ instantly gives acetate a Kb of 1.0 × 10⁻¹⁴ / 1.8 × 10⁻⁵ = 5.6 × 10⁻¹⁰, an extremely feeble base, exactly as expected from a strong-ish weak acid.

The relation encodes chemistry's most useful see-saw: the stronger the acid, the weaker its conjugate base, and the product is fixed. It also explains why sodium acetate solutions are mildly alkaline while sodium chloride solutions are neutral: chloride's parent HCl is so strong that its conjugate Kb is vanishingly small. Kw itself is temperature-dependent (1.0 × 10⁻¹⁴ at 25 °C but about 5.5 × 10⁻¹⁴ at 50 °C), so the pairing of tabulated Ka and Kb values only balances at the temperature they were measured.

Worked example 4.3. Given KaK_a = 1.8e-5, KwK_w = 1.0e-14; find KbK_b (base dissociation constant of the conjugate). Acetate Kb from acetic acid Ka 1.8e-5 → 5.5556e-10.

4.4 pKa from Acid Dissociation Constant

Solve it online →formula.expert/solvers/pka-from-ka
(Chemistry 12-30)pKa=−log⁡10Ka\mathrm{p}K_a = -\log_{10} K_a
Where
  • pKa\mathrm{p}K_a= pKa
  • KaK_a= Acid dissociation constant

Acid strengths span more than twenty orders of magnitude, so chemists do to Ka exactly what Sørensen did to [H⁺]: take the negative logarithm. Acetic acid's Ka of 1.8 × 10⁻⁵ becomes pKa 4.74, hydrofluoric acid's 6.8 × 10⁻⁴ becomes 3.17, and formic acid's 1.8 × 10⁻⁴ becomes 3.75: three numbers you can hold in your head and compare at a glance. Lower pKa means stronger acid, and every unit is a tenfold jump in dissociation.

The sign is the perennial trip-up: because Ka is smaller than one for every weak acid, its logarithm is negative and the minus sign flips pKa positive. A pKa of 3.75 corresponds to Ka = 10⁻³·⁷⁵ = 1.78 × 10⁻⁴, not 10³·⁷⁵. pKa also does double duty as a practical marker: it is the pH at which an acid is exactly half ionised, which is why pharmacologists read a drug's pKa straight off the label to predict whether it will cross a membrane in the stomach (pH 2) or the small intestine (pH 7).

Worked example 4.4. Given KaK_a = 1.8e-5; find pKa\mathrm{p}K_a (pka). Acetic acid Ka = 1.8e-5 → pKa = 4.74473.

4.5 pKb from Base Dissociation Constant

Solve it online →formula.expert/solvers/pkb-from-kb
(Chemistry 12-31)pKb=−log⁡10Kb\mathrm{p}K_b = -\log_{10} K_b
Where
  • pKb\mathrm{p}K_b= pKb
  • KbK_b= Base dissociation constant

Kb measures how far a base pulls a proton off water, and taking its negative logarithm produces the same compact scale that pKa gives on the acid side: small pKb means a strong base. Methylamine, with Kb = 4.4 × 10⁻⁴, has pKb = 3.36 and is a distinctly stronger base than ammonia at Kb = 1.8 × 10⁻⁵ and pKb 4.74: the extra electron density from the methyl group is worth more than a full order of magnitude.

Modern practice increasingly skips pKb entirely and quotes the pKa of the conjugate acid instead, since a single acid scale ranks everything from sulfuric acid to hydroxide without ever switching frameworks. The two are locked together by pKa + pKb = 14 at 25 °C, so a base of pKb 9.25 has a conjugate acid of pKa 4.75. Just remember that identity, like pH + pOH = 14, holds only near room temperature: Kw climbs with heat, and at 60 °C the sum is closer to 13.0.

Worked example 4.5. Given KbK_b = 4.4e-4; find pKb\mathrm{p}K_b (pkb). Methylamine Kb = 4.4e-4 → pKb = 3.35655.

(Chemistry 12-32)pH=−log⁡10Ka C\mathrm{pH} = -\log_{10}\sqrt{K_a\,C}
Where
  • pH\mathrm{pH}= pH of the solution
  • KaK_a= Acid dissociation constant
  • CC= Formal acid concentration (M)
CKapH
Figure 4.6: ph of a weak acid from ka.

For a weak acid HA the equilibrium expression Ka = x²/(C − x) is a quadratic, but when the acid barely dissociates the x in the denominator is negligible and it collapses to x = [H⁺] = √(Ka·C). Take 0.100 M acetic acid with Ka = 1.8 × 10⁻⁵: [H⁺] = √(1.8 × 10⁻⁶) = 1.34 × 10⁻³ M, so pH = 2.87. That is a thousand times less acidic than 0.100 M HCl at pH 1.00: the whole difference between a weak acid and a strong one at the same concentration.

The approximation earns its keep but has a known failure mode. It assumes the dissociated fraction is under about 5%, which holds when C is at least a hundred times Ka. Push a fairly strong weak acid to low concentration (0.0010 M chloroacetic acid, Ka = 1.4 × 10⁻³) and the square-root shortcut overshoots badly; you must solve the quadratic. It also ignores water's own contribution to [H⁺], which starts to matter for very dilute or very weak acids where the predicted pH creeps above about 6.5.

Worked example 4.6. Given KaK_a = 1.8e-5, CC = 0.100 M; find pH\mathrm{pH} (ph of the solution). 0.100 M acetic acid (Ka 1.8e-5) → pH 2.87236.

(Chemistry 12-33)% ion=[H+]C×100%\%\,\text{ion} = \frac{[\mathrm{H^+}]}{C} \times 100\%
Where
  • % ion\%\,\text{ion}= Percent ionization (%)
  • [H+][\mathrm{H^+}]= Hydrogen ion concentration at equilibrium (M)
  • CC= Formal acid concentration (M)
C[H+]% ion
Figure 4.7: percent ionization of a weak acid.

Ka tells you how a weak acid behaves in principle; percent ionization tells you what actually happened in the beaker. In 0.100 M acetic acid the equilibrium [H⁺] is 1.34 × 10⁻³ M, so only 1.34% of the molecules have given up a proton and 98.7% are still intact: a vivid picture of what "weak" means. It is also the number that justifies the x-is-small approximation, which is generally trusted below about 5% ionization.

The counterintuitive part is that percent ionization rises as you dilute. Because [H⁺] goes as the square root of concentration while C goes linearly, halving the concentration multiplies the fraction ionized by roughly √2. Dilute that acetic acid to 0.0010 M and it is about 13% ionized even though the solution is far less acidic in absolute terms. Ostwald's dilution law captures the same effect, and it is why a weak acid approaches complete dissociation in the limit of infinite dilution.

Worked example 4.7. Given [H+][\mathrm{H^+}] = 1.34e-3 M, CC = 0.100 M; find % ion\%\,\text{ion} (percent ionization). [H+] 1.34e-3 in 0.100 M acid → 1.34% ionized.

4.8 Henderson–Hasselbalch Equation (Weak Acid Buffer)

Solve it online →formula.expert/solvers/henderson-hasselbalch-acid
(Chemistry 12-34)pH=pKa+log⁡10 ⁣[A−][HA]\mathrm{pH} = \mathrm{p}K_a + \log_{10}\!\frac{[\mathrm{A^-}]}{[\mathrm{HA}]}
Where
  • pH\mathrm{pH}= pH of the buffer
  • pKa\mathrm{p}K_a= pKa of the weak acid
  • [A−][\mathrm{A^-}]= Conjugate base concentration (M)
  • [HA][\mathrm{HA}]= Weak acid concentration (M)
[A−][HA]pHpKa
Figure 4.8: henderson–hasselbalch equation (weak acid buffer).

A buffer resists pH change because it holds a reservoir of both a weak acid and its conjugate base: add acid and the base mops it up, add base and the acid neutralises it. The Henderson–Hasselbalch equation says the pH depends only on the acid's pKa and the ratio of the two forms, not on how concentrated they are. Equal amounts give pH = pKa exactly, which is why you choose a buffer whose pKa sits within about one unit of your target. Acetic acid has pKa 4.76, so an acetate buffer holding 0.200 M acetate against 0.100 M acetic acid sits at pH = 4.76 + log₁₀(2) = 4.76 + 0.301 = 5.06.

Lawrence Joseph Henderson, a Harvard physiologist, wrote the mass-action version in 1908 while working out how blood keeps its pH steady; Karl Albert Hasselbalch, a Dane, recast it in logarithms in 1917 using Sørensen's brand-new pH scale, and the joint name stuck. Their subject remains the textbook example: blood's bicarbonate system has an effective pKa of 6.10 and runs at a 20:1 ratio of HCO₃⁻ to dissolved CO₂, giving 6.10 + log₁₀(20) = 7.40, the pH your body defends to within about 0.05 units. The classic trap is that the equation is an approximation built on assuming the acid and base concentrations are their formal (added) values; it fails for very dilute buffers, for pH far from pKa, and it never applies to a strong acid, which has no meaningful pKa to work with.

Worked example 4.8. Given pKa\mathrm{p}K_a = 4.76, [A−][\mathrm{A^-}] = 0.200 M, [HA][\mathrm{HA}] = 0.100 M; find pH\mathrm{pH} (ph of the buffer). Acetate buffer 0.200 M / 0.100 M at pKa 4.76 → pH 5.0610.

4.9 Henderson–Hasselbalch Equation (Weak Base Buffer)

Solve it online →formula.expert/solvers/henderson-hasselbalch-base
(Chemistry 12-35)pOH=pKb+log⁡10 ⁣[BH+][B]\mathrm{pOH} = \mathrm{p}K_b + \log_{10}\!\frac{[\mathrm{BH^+}]}{[\mathrm{B}]}
Where
  • pOH\mathrm{pOH}= pOH of the buffer
  • pKb\mathrm{p}K_b= pKb of the weak base
  • [BH+][\mathrm{BH^+}]= Conjugate acid concentration (M)
  • [B][\mathrm{B}]= Weak base concentration (M)
[BH+][B]pOHpKb
Figure 4.9: henderson–hasselbalch equation (weak base buffer).

Run Henderson and Hasselbalch's argument on the base side and everything mirrors: pOH is set by the base's pKb plus the logarithm of the conjugate-acid-to-base ratio. An ammonia buffer (pKb 4.75) holding 0.200 M NH₄⁺ against 0.100 M NH₃ has pOH = 4.75 + log₁₀(2) = 5.05, so at 25 °C its pH is 14 − 5.05 = 8.95: comfortably alkaline, which is why ammonia/ammonium buffers are the standard choice for EDTA titrations of calcium and magnesium hardness.

The one thing to keep straight is which species goes on top. In the acid form the base is the numerator; here the conjugate acid is, because adding more BH⁺ makes the solution less basic. Get it upside down and your answer is wrong by twice the log term. Many chemists sidestep the whole issue by converting pKb to pKa (pKa = 14 − pKb at 25 °C) and using the acid form throughout: for ammonia that gives pKa(NH₄⁺) = 9.25, and 9.25 + log₁₀(0.100/0.200) = 8.95, the same answer by a different road.

Worked example 4.9. Given pKb\mathrm{p}K_b = 4.75, [BH+][\mathrm{BH^+}] = 0.200 M, [B][\mathrm{B}] = 0.100 M; find pOH\mathrm{pOH} (poh of the buffer). Ammonia buffer 0.200 M NH4+ / 0.100 M NH3 → pOH 5.0510.

(Chemistry 12-36)C1V1=C2V2C_1 V_1 = C_2 V_2
Where
  • C1C_1= Initial concentration (M)
  • V1V_1= Initial volume (L)
  • C2C_2= Final concentration (M)
  • V2V_2= Final volume (L)
C1V1C2V2
Figure 4.10: dilution equation (c1v1 = c2v2).

Adding solvent to a solution spreads the same solute through a larger volume: the moles do not change, only their crowding. Since moles equal concentration times volume, C1V1C_1V_1 must equal C2V2C_2V_2 before and after any dilution. To prepare 250 mL of 1.0 M hydrochloric acid from a 12.1 M concentrated stock, solve for V1V_1: (1.0 × 250)/12.1 ≈ 20.7 mL of stock, made up to the 250 mL mark with water. (And always add acid to water, never the reverse.)

The law is not limited to molarity: any concentration measure proportional to moles per volume works, as long as both sides use the same one. Water-treatment operators lean on it daily when dosing inhibitor or biocide from concentrated drums into recirculating loops, and biologists use the identical arithmetic for serial dilutions, where each step divides concentration by a fixed factor.

Worked example 4.10. Given C1C_1 = 6.00 M, V1V_1 = 50.0 mL, V2V_2 = 300.0 mL; find C2C_2 (final concentration). 50 mL of 6.0 M diluted to 300 mL → 1.0 mol/L.

4.11 Titration: Concentration of an Unknown

Solve it online →formula.expert/solvers/titration-molarity
(Chemistry 12-37)Ca=n CbVbVaC_a = \frac{n\,C_b V_b}{V_a}
Where
  • CaC_a= Analyte concentration (M)
  • VaV_a= Analyte volume (aliquot) (L)
  • CbC_b= Titrant concentration (M)
  • VbV_b= Titre volume delivered (L)
  • nn= Mole ratio (analyte per titrant)
VbCbnCaVa
Figure 4.11: titration: concentration of an unknown.

At the equivalence point the moles of titrant delivered, CbVbC_b V_b, exactly match the moles of analyte present, CaVaC_a V_a, scaled by the balanced equation's mole ratio n. Everything else in a titration (the burette, the indicator, the swirling) exists only to find that point precisely. Titrate a 25.00 mL aliquot of hydrochloric acid with 0.1000 M sodium hydroxide and take 23.45 mL to reach the endpoint: with n = 1, CaC_a = (1 × 0.1000 × 23.45)/25.00 = 0.09380 M, good to four figures from nothing but glassware.

The mole ratio is where marks are lost. For a diprotic acid such as H₂SO₄ titrated with NaOH, one mole of acid consumes two of base, so n = 0.5: a 25.00 mL aliquot needing 30.00 mL of 0.100 M NaOH is 0.5 × 0.100 × 30.00/25.00 = 0.0600 M. Karl Friedrich Mohr systematised the whole technique in his 1855 Lehrbuch der chemisch-analytischen Titrirmethode, introducing the burette clamp and the pinchcock that made reproducible volumetric analysis possible; his methods still underpin water-hardness and chlorine testing today. Note the difference between the endpoint (where the indicator changes) and the equivalence point (where the stoichiometry balances): the gap between them is the indicator error, which is why the indicator is chosen to change colour on the steep part of the titration curve.

Worked example 4.11. Given VaV_a = 25.00 mL, CbC_b = 0.1000 M, VbV_b = 23.45 mL, nn = 1; find CaC_a (analyte concentration). 25.00 mL HCl vs 23.45 mL of 0.1000 M NaOH → 0.09380 M.

Module 4 practice

39. The pH scale: A standardised buffer in the stockroom is labelled: hydrogen-ion concentration 1 × 10⁻³ mol/L. Calculate the pH of the sample.

40. The pH scale: A rainwater sample caught off the science-wing roof measures 8.0 × 10⁻⁵ mol/L in hydrogen ion. Determine the pH of the sample, to two decimal places.

41. The Kw family: A weak monoprotic acid used in a titration practical has an acid dissociation constant of Ka = 1.0 × 10⁻⁹ at 25 °C. Calculate the acid's pKa.

42. The Kw family: A weak acid HA has Ka = 8.0 × 10⁻⁹ at 25 °C, where the ion product of water is Kw = 1.0 × 10⁻¹⁴. Its conjugate base A⁻ is the species left behind once the proton has gone. Determine Kb for the conjugate base A⁻ — the hypochlorite-style partner of this acid.

43. Weak acids and ICE: A weak monoprotic acid HA, Ka = 2.0 × 10⁻⁶, is made up to a formal concentration of 0.020 mol/L at 25 °C. Less than 5 % of it ionizes, so the x-is-small approximation applies. Calculate the pH of the solution.

44. Weak acids and ICE: The same weak acid HA (Ka = 8.0 × 10⁻⁶) sits at a formal concentration of 0.020 mol/L. A pH meter puts the equilibrium hydrogen-ion concentration at 4.0 × 10⁻⁴ mol/L. Calculate the percent ionization of the acid.

45. Buffer country: A buffer holding 1.00 mol/L of a conjugate base A⁻ and 0.200 mol/L of its weak acid HA reads pH 7.90 on a calibrated meter at 25 °C. Determine the pKa of the weak acid.

46. Buffer country: A buffer is made from hydrazine (pKb 5.89) and its conjugate acid, supplied as hydrazinium chloride. The flask holds 1.60 mol/L of the conjugate acid BH⁺ and 0.200 mol/L of the free base B, at 25 °C. Determine the buffer's pOH, and then its pH.

47. Dilution discipline: A protocol calls for 0.200 mol of solute to be delivered from a 0.400 mol/L stock solution. Determine the volume of stock the protocol requires.

48. Dilution discipline: A technician pipettes 40.0 mL of 1.50 mol/L stock into a volumetric flask and makes the contents up to a final volume of 200.0 mL with distilled water. Calculate the concentration of the diluted solution.

49. The burette: A 50.0 mL aliquot of hydrochloric acid of unknown concentration is pipetted into a conical flask with two drops of indicator. From the burette, 0.100 mol/L sodium hydroxide brings the flask to a lasting colour change after 30.0 mL. Acid and base react one-to-one, so n = 1. Determine the concentration of the acid.

50. The burette: The same titration, marked the long way: a 25.0 mL aliquot of a monoprotic acid takes 30.0 mL of 0.100 mol/L sodium hydroxide to reach the endpoint, one-to-one. This time the examiner wants the moles shown. Determine the amount of base delivered, then the acid's concentration.

51. The Titration Final: The last station of the practical exam. A 1.00 mol/L stock of sodium hydroxide is too strong to titrate with, so 10.0 mL of it is pipetted into a volumetric flask and made up to 500.0 mL. That diluted base then titrates a 50.0 mL aliquot of hydrochloric acid — strong, fully dissociated, one-to-one — and the endpoint lands at exactly 25.0 mL. Every number is chosen to work in your head, and every answer feeds the next line. Determine the acid's concentration, its pH, and its pOH — one line at a time.

52. The Titration Final: Bonus mark, and a decision to sign off on. The rinse water left in the flask is a weak monoprotic acid, formal concentration 0.010 mol/L, Ka = 1.0 × 10⁻⁶, ionizing well under 5 %. The building's discharge permit sets a floor of pH 2.50: anything more acidic than that must go to the neutralizing tank instead of the drain. Determine the rinse water's pH, then rule on where it goes.

Module 5

Electrochemistry

Reading the table · Nernst, off standard · Charge on the clock · Faraday's scales · Time to plate · The Electroplating Shift

In BC Chemistry 12 · Alberta Chemistry 30 · Ontario SCH4U

(Chemistry 12-38)Ecell∘=Ecathode∘−Eanode∘E^{\circ}_{\text{cell}} = E^{\circ}_{\text{cathode}} - E^{\circ}_{\text{anode}}
Where
  • Ecell∘E^{\circ}_{\text{cell}}= Standard cell potential (V)
  • Ecathode∘E^{\circ}_{\text{cathode}}= Cathode standard reduction potential (V)
  • Eanode∘E^{\circ}_{\text{anode}}= Anode standard reduction potential (V)
E°cellE°anodeE°cathode
Figure 5.1: standard cell potential from half-cells.

Every half-cell potential in the standard tables is quoted as a reduction potential against the standard hydrogen electrode, arbitrarily pinned at 0.000 V. To assemble a cell, pick which electrode is reduced (the cathode) and subtract the other's tabulated value: the Daniell cell puts Cu²⁺/Cu at +0.34 V against Zn²⁺/Zn at −0.76 V, giving 0.34 − (−0.76) = 1.10 V. A positive result means the cell runs spontaneously as written; a negative one means you have the electrodes backwards.

Two traps catch almost everyone. First, do not flip the sign of the anode value before subtracting: the minus in the formula already does that, and doing it twice cancels the reaction. Second, never multiply a half-cell potential by its stoichiometric coefficient: potential is energy per coulomb, an intensive property, so balancing 2Ag⁺ + Cu → 2Ag + Cu²⁺ leaves silver's +0.80 V untouched and the cell delivers 0.80 − 0.34 = 0.46 V. It is ΔG = −nFE°, not E° itself, that scales with the amount of reaction.

Worked example 5.1. Given Ecathode∘E^{\circ}_{\text{cathode}} = 0.34 V, Eanode∘E^{\circ}_{\text{anode}} = -0.76 V; find Ecell∘E^{\circ}_{\text{cell}} (standard cell potential). Daniell cell: +0.34 V cathode, -0.76 V anode → 1.10 V.

(Chemistry 12-39)E=E∘−RTnFln⁡QE = E^{\circ} - \frac{RT}{nF}\ln Q
Where
  • EE= Cell potential (V)
  • E∘E^{\circ}= Standard cell potential (V)
  • nn= Electrons transferred
  • QQ= Reaction quotient
  • TT= Absolute temperature (°C)
EE°nQT
Figure 5.2: nernst equation.

A tabulated standard potential assumes every dissolved species sits at 1 M and every gas at 1 bar: conditions almost nothing in the real world satisfies. Walther Nernst's 1889 equation supplies the correction: the potential shifts by (RT/nF) ln Q, pushing the cell voltage up when reactants are plentiful and down as products pile up. At 25 °C the factor RT/F is 0.02569 V, so multiplying by ln 10 gives the famous 0.05916/n volts per decade. A Daniell cell with E° = 1.10 V, n = 2, and Q = 0.100 reads E = 1.10 + (0.05916/2) = 1.130 V.

That "59 mV per tenfold" is the entire basis of potentiometry. A glass pH electrode is a concentration cell whose voltage moves 59 mV for every pH unit, which is exactly why a pH meter must be calibrated at the temperature of the sample: at 50 °C the slope is 64 mV, not 59, and an uncorrected reading drifts. Nernst received the 1920 Nobel Prize in Chemistry (presented in 1921) chiefly for his heat theorem, the third law of thermodynamics, but this equation is what carries his name into every teaching lab. The usual mistakes are writing Q upside down (products over reactants, always) and swapping ln for log₁₀ without changing 0.02569 to 0.05916.

Worked example 5.2. Given E∘E^{\circ} = 1.10 V, nn = 2, QQ = 0.100, TT = 25 °C; find EE (cell potential). Daniell cell E0 1.10 V, n=2, Q=0.100 at 25 C → E = 1.12958 V.

(Chemistry 12-40)Q=ItQ = I t
Where
  • QQ= Charge (C)
  • II= Current (A)
  • tt= Time (s)
IQt
Figure 5.3: electric charge (q = it).

Current is not a thing that flows. It is a rate (the amount of charge passing a chosen cross-section of the conductor each second) and one ampere means one coulomb per second. Once that is clear, Q=ItQ = It needs no proof, because it is the definition read backwards: if charge crosses at a steady rate, the total that crossed is the rate multiplied by how long it kept up. The only condition the equation imposes is the word steady. A current that varies has to be integrated, Q=∫I dtQ = \int I\,dt, and this page is the special case where the integral collapses to a rectangle.

A 2 A charger running for one hour moves 2×3600=7200 C2 \times 3600 = 7200\ \text{C}. Battery ratings are the same arithmetic wearing different units: a phone cell marked 3000 mAh holds 3 Ah, and 3×3600=10 800 C3 \times 3600 = 10\,800\ \text{C} of deliverable charge. Divide by the elementary charge, 1.602×10−191.602 \times 10^{-19} C, and that is about 6.7×10226.7 \times 10^{22} electrons: a number that only sounds absurd until you remember a gram of copper contains ten times as many free ones already sitting in the metal, drifting at well under a millimetre per second.

Since the 2019 redefinition of the SI, this relation is closer to the foundation than it used to be. The ampere is now fixed by declaring the elementary charge to be exactly 1.602176634×10−191.602176634 \times 10^{-19} C, which makes the coulomb a count of charges and the ampere a count per second. Michael Faraday got there experimentally in the 1830s: his laws of electrolysis measure the charge needed to plate out a mole of a substance, and that constant, 96 485 C per mole, is nothing but Q=ItQ = It run on a plating tank. Electroplating, anodising and battery capacity testing all still bill in ampere-hours for exactly this reason.

Two errors are worth naming, and one convention deserves an apology. The first error is treating milliamp-hours as energy. They are charge; a 3000 mAh cell at 3.7 V holds 3×3.7=11.1 Wh3 \times 3.7 = 11.1\ \text{Wh}, and the same 3000 mAh at 1.2 V holds a third of that, so comparing two batteries by mAh alone tells you very little. The second is applying the equation to a current that is not constant: a motor's inrush, a switching supply's chopped input, or anything on AC, where over a full cycle the net charge transferred is zero even though the current is real all along. As for the convention: current is drawn flowing from plus to minus, while in a metal the electrons actually travel the other way. Benjamin Franklin guessed the sign in the 1750s, a century before anyone knew a charge carrier existed, and he guessed wrong. Nothing in the physics breaks (a deficit of negatives moving left is indistinguishable from positives moving right) but it is a historical accident, not a discovery, and it is worth knowing that it is one.

Worked example 5.3. Given II = 2 A, tt = 30 s; find QQ (charge). 2 A for 30 s → 60 C.

5.4 Faraday's Law of Electrolysis (m = QM/nF)

Solve it online →formula.expert/solvers/faraday-electrolysis-mass
(Chemistry 12-41)m=QMnFm = \frac{Q M}{n F}
Where
  • mm= Mass deposited or dissolved (g)
  • QQ= Charge passed (C)
  • MM= Molar mass of the deposited element (g/mol)
  • nn= Electrons transferred per ion
QmMn
Figure 5.4: faraday's law of electrolysis (m = qm/nf).

Electroplating is stoichiometry done with a wire. Charge Q divided by the Faraday constant F = 96 485 C/mol gives the moles of electrons pushed through the cell; divide by n, the electrons each ion needs, and you have moles of metal; multiply by the molar mass M and you have grams on the cathode. Charge is usually the thing you control indirectly, through Q = It, so a steady current for a measured time is all the input a plating shop needs.

Michael Faraday established this in 1833–34 with nothing but jars, wires and a balance, and the vocabulary you use to describe it is his. He was uneasy with the existing terms, which assumed electricity was a fluid being carried, so he wrote to William Whewell at Cambridge asking for better ones. Whewell supplied Greek: ion, "that which goes"; anode, the way up; cathode, the way down; electrode, anion, cation, electrolyte. Faraday adopted the lot. What his measurements really showed (that a fixed quantity of electricity always liberates a fixed chemical equivalent) was the first hard evidence that charge itself comes in fixed lumps, sixty years before J. J. Thomson found the electron.

Worked case: copper plating, Cu²⁺ + 2e⁻ → Cu, with M = 63.55 g/mol and n = 2. Run 2.00 A for 30.0 minutes and Q = 2.00 × 1800 = 3600 C (exactly 1 A·h). Then m = 3600 × 63.55/(2 × 96 485) = 1.186 g of copper. Note that the same 3600 C would deposit 4.02 g of silver, because Ag⁺ needs only one electron and carries a heavier atom: the whole reason Faraday's "electrochemical equivalents" differ from element to element.

Worked example 5.4. Given QQ = 1 Ah, MM = 63.55 g/mol, nn = 2 ; find mm (mass deposited or dissolved). Copper plating, 1 Ah at M = 63.55 g/mol, n = 2 → 1.1856 g.

Module 5 practice

53. Reading the table: A voltaic cell pairs a lead half-cell, Pb²⁺(aq) + 2e⁻ → Pb(s) at −0.13 V, with a second half-cell whose metal has rubbed off the label. The lead electrode is the cathode, and at standard conditions the cell delivers 0.32 V. Determine the standard reduction potential of the anode half-cell.

54. Reading the table: A voltaic cell pairs a lead half-cell, Pb²⁺(aq) + 2e⁻ → Pb(s) at −0.13 V, with a second half-cell whose metal has rubbed off the label. The lead electrode is the cathode, and at standard conditions the cell delivers 0.13 V. Determine the standard reduction potential of the anode half-cell.

55. Nernst, off standard: A nickel–silver cell operates at 25 °C. Its balanced cell reaction is Ni(s) + 2Ag⁺(aq) → Ni²⁺(aq) + 2Ag(s), and at standard conditions it delivers 1.06 V. In the working cell the Ni²⁺ solution is 0.0010 mol/L and the Ag⁺ solution is 1.0 mol/L. Calculate the cell potential under these conditions.

56. Nernst, off standard: A zinc–copper cell operates at 25 °C. Its balanced cell reaction is Zn(s) + Cu²⁺(aq) → Zn²⁺(aq) + Cu(s), and at standard conditions it delivers 1.10 V. In the working cell the Zn²⁺ solution is 0.10 mol/L and the Cu²⁺ solution is 1.0 mol/L. Calculate the cell potential under these conditions.

57. Charge on the clock: An electrolytic cell in a school lab draws a steady 9.0 A for 10 min. Calculate the charge that passes through the cell.

58. Charge on the clock: An industrial rectifier holds 8.0 A through a cell for 2.0 h without interruption. Determine the total charge passed.

59. Faraday's scales: An electrolytic cell plates aluminum from a bath of Al³⁺ ions onto a steel blank. A coulometer records 57900 C through the cell. The molar mass of aluminum is 27.0 g/mol, and F = 96 500 C/mol. Calculate the mass of aluminum deposited.

60. Faraday's scales: An electrolytic cell plates zinc from a bath of Zn²⁺ ions onto a steel blank. A coulometer records 19300 C through the cell. The molar mass of zinc is 65.4 g/mol, and F = 96 500 C/mol. Calculate the mass of zinc deposited.

61. Time to plate: A work order calls for 38.1 g of copper on a batch of parts, and the line has a 100 min window to do it in. The bath carries Cu²⁺ ions, copper has a molar mass of 63.5 g/mol, and F = 96 500 C/mol. Determine the current the rectifier must hold.

62. Time to plate: A plating line runs a rack of parts through a copper bath at a steady 9.65 A for 50 min. The bath carries Cu²⁺ ions, copper has a molar mass of 63.5 g/mol, and F = 96 500 C/mol. Calculate the mass of copper deposited on the rack.

63. The Electroplating Shift: Last rack of the shift. A nickel plating cell runs from a bath of Ni²⁺ ions with inert anodes, where water is oxidized. The data sheet gives Ni²⁺(aq) + 2e⁻ → Ni(s) at −0.26 V and O₂(g) + 4H⁺(aq) + 4e⁻ → 2H₂O(l) at +1.23 V. The rectifier holds 19.3 A for 50 min, nickel has a molar mass of 58.7 g/mol, and F = 96 500 C/mol. The work order will not ship unless the rack carries at least 14.1 g. Work each line — every answer feeds the next. Determine whether this shift meets the work order, one line at a time.

64. The Electroplating Shift: Bonus mark, worked backwards. A test coupon comes off the same line 17.67 g heavier after 57900 C passed through an unlabelled cobalt bath. The molar mass of cobalt is 58.9 g/mol, and F = 96 500 C/mol. Determine how many electrons each ion in that bath took.

Module 6

Gases & Solutions

The three gas laws · Combined and ideal · Molar mass from the gas · Partial pressures · Graham's race · Three ways to say how much · Colligative counting · Vapour pressure stories · The Gas Works

(Chemistry 12-42)P1V1=P2V2P_1 V_1 = P_2 V_2
Where
  • P1P_1= Initial pressure (kPa)
  • V1V_1= Initial volume (L)
  • P2P_2= Final pressure (kPa)
  • V2V_2= Final volume (L)
P1V1P2V2
Figure 6.1: boyle's law.

Robert Boyle published his gas law in 1662, making it one of the oldest quantitative laws in physics: at constant temperature, the pressure and volume of a trapped gas are inversely proportional, so their product never changes. Cap a syringe and squeeze: compress 60 mL of air at 100 kPa down to 20 mL and the pressure climbs to 300 kPa. Molecularly, shrinking the space raises how often molecules hammer the walls, and pressure rises in exact proportion.

The law matters wherever gas gets squeezed. Scuba divers learn it first: air breathed at depth expands as they ascend, which is why the cardinal rule is never to hold your breath on the way up. Boyle's law assumes the temperature and the amount of gas stay fixed; change either and you need Charles's law or the combined gas law instead.

Worked example 6.1. Given P1P_1 = 1 atm, V1V_1 = 2 L, P2P_2 = 4 atm; find V2V_2 (final volume). 2 L at 1 atm → 4 atm gives 0.5 L.

(Chemistry 12-43)V1T1=V2T2\frac{V_1}{T_1} = \frac{V_2}{T_2}
Where
  • V1V_1= Initial volume (L)
  • T1T_1= Initial absolute temperature (°C)
  • V2V_2= Final volume (L)
  • T2T_2= Final absolute temperature (°C)
V1T1V2T2
Figure 6.2: charles's law.

Hold the pressure on a gas constant and its volume follows its absolute temperature in strict proportion: warm it by 10% and it swells by 10%. The reason is worth having rather than memorising. Temperature is a measure of how fast the molecules are moving; pressure is how hard their impacts push on each square metre of wall. If the gas is to keep pushing with the same force while its molecules move faster, the only thing it can do is spread out, so that each patch of wall is struck less often. Volume rises exactly as fast as temperature to keep that balance, and V1/T1=V2/T2V_1/T_1 = V_2/T_2 is that sentence in symbols.

A 2.5 L balloon leaves a 22 °C room and goes into a −18 °C freezer. In kelvin those are 295.15 and 255.15, so V2=2.5×255.15/295.15=2.16 LV_2 = 2.5 \times 255.15/295.15 = 2.16\ \text{L}: it loses about 14% of its volume and visibly puckers. Bring it back out and it recovers. Nothing left the balloon; the same molecules simply stopped needing as much room.

Jacques Charles found this with hydrogen balloons around 1787 and never published it. Joseph Louis Gay-Lussac did the careful work and published in 1802, and generously named the result after Charles. The interesting part is what came out of extending the straight line. Plot volume against Celsius temperature and you get a line that, extrapolated backwards, hits zero volume at about −273 °C. No one in 1802 could reach anywhere near that temperature, yet the graph pointed straight at it. That extrapolation is how absolute zero was first located, and it is why William Thomson could propose an absolute scale in 1848 by simply moving the origin to where the gases were pointing. The modern value, −273.15 °C, is the zero of the kelvin scale.

Which is exactly why a ratio in Celsius is meaningless here. Going from 20 °C to 40 °C does not double the volume; in kelvin that is 293.15 to 313.15, a rise of under 7%. Worse, a Celsius ratio breaks outright when the temperature crosses zero: 0 °C in the denominator gives infinity, and a negative Celsius temperature gives a negative volume. This page converts your °C or °F entries to kelvin before it does anything, but the trap is worth recognising when you meet the equation off-screen.

Two smaller conditions do real work. The pressure must actually be constant: a gas sealed in a rigid tank obeys Gay-Lussac's law instead, where pressure rises and volume does not move at all. And the gas must stay a gas. Cool steam through 100 °C and the relation does not merely become inaccurate, it stops applying: the vapour condenses and the volume collapses by a factor of about 1600. A balloon is also only approximately constant-pressure, since the stretched rubber adds a little tension of its own, which is why the real shrinkage runs slightly under what the arithmetic predicts.

Worked example 6.2. Given V1V_1 = 2 L, T1T_1 = 300 K, T2T_2 = 600 K; find V2V_2 (final volume). 2 L at 300 K heated to 600 K → 4 L.

(Chemistry 12-44)P1T1=P2T2\frac{P_1}{T_1} = \frac{P_2}{T_2}
Where
  • P1P_1= Initial pressure (kPa)
  • T1T_1= Initial absolute temperature (°C)
  • P2P_2= Final pressure (kPa)
  • T2T_2= Final absolute temperature (°C)
P1T1P2T2
Figure 6.3: gay-lussac's law.

Seal a gas in a container that cannot change size and there is only one thing left for it to do when you heat it: push harder. Pressure then tracks absolute temperature in direct proportion, P1/T1=P2/T2P_1/T_1 = P_2/T_2. The mechanism is the same one behind Charles's law with the outcome swapped. Faster molecules strike the walls both more often and with more momentum each time, and since the walls will not move aside, all of that arrives as pressure.

Here is the case everyone actually meets, worked carefully, because the careless version is the standard error. A tire is set to 220 kPa gauge on a 5 °C morning and warms to 45 °C after an hour on the highway. Convert to absolute pressure first: 220 + 101 = 321 kPa absolute. Then P2=321×318.15/278.15=367 kPaP_2 = 321 \times 318.15/278.15 = 367\ \text{kPa} absolute, which is 266 kPa on the gauge: a rise of 46 kPa, about 6.6 psi. Run the same calculation on the gauge reading alone and you get 252 kPa, understating the rise by a third. This is why tire pressures are specified cold, and why topping up a hot tire leaves it soft in the morning.

The relation is usually credited to Gay-Lussac's 1802 paper, though Guillaume Amontons had it a century earlier: around 1702 he built an air thermometer that worked on precisely this principle, and noticed that the pressure line extrapolated toward a temperature below which it could not go. Some texts call it Amontons's law for that reason. Combine it with Boyle's law and Charles's law and you have the combined gas law; add Avogadro and you have PV=nRTPV = nRT, of which this is the constant-volume slice.

Absolute pressure is the trap here, more than absolute temperature. The ratio P1/P2P_1/P_2 is only meaningful when both pressures are measured from vacuum, because the equation is counting molecular impacts and a gauge has quietly subtracted an atmosphere from the count. Temperature has the same requirement for the same reason (kelvin, not Celsius) and this page converts your entries on both fronts. But when you meet the equation on paper, ask twice whether the pressure in your hand is gauge or absolute. It usually is gauge; almost every instrument in a mechanical room reads that way.

The other honest limit is that constant volume is an idealisation. A tire is not rigid: it grows a little as it warms, which relieves some of the pressure rise, so the measured increase runs slightly below the calculation. A steel cylinder is much closer to the ideal, which is what makes this law genuinely dangerous rather than merely academic. An aerosol can left on a dashboard, a propane cylinder in a closed vehicle, or a sealed pressure vessel in a fire all follow this line with nothing to relieve them, and the pressure keeps climbing until something gives. Relief valves exist because the equation has no upper bound.

Worked example 6.3. Given P1P_1 = 3 atm, T1T_1 = 300 K, T2T_2 = 400 K; find P2P_2 (final pressure). 3 atm at 300 K heated to 400 K → 4 atm (405.3 kPa).

(Chemistry 12-45)P1V1T1=P2V2T2\frac{P_1 V_1}{T_1} = \frac{P_2 V_2}{T_2}
Where
  • P1P_1= Initial pressure (kPa)
  • V1V_1= Initial volume (L)
  • T1T_1= Initial absolute temperature (°C)
  • P2P_2= Final pressure (kPa)
  • V2V_2= Final volume (L)
  • T2T_2= Final absolute temperature (°C)
P1V1T1P2T2V2
Figure 6.4: combined gas law.

The combined gas law merges Boyle's, Charles's, and Gay-Lussac's laws into a single statement: for a fixed amount of gas, PV/T is constant. A weather balloon shows all three variables moving at once. Launched with 2.0 m³ of helium at 101 kPa and 288 K, it rises to where the pressure is 30 kPa and the temperature 228 K; its new volume is V₂ = P₁V₁T₂ ÷ (P₂T₁) = 2.0 × 101 × 228 ÷ (30 × 288) ≈ 5.3 m³: more than double.

Hold any one variable constant and the named laws drop out: fix T for Boyle's law, fix P for Charles's, fix V for Gay-Lussac's. Temperatures must be absolute (the ratio of 20 °C to 40 °C is not 1:2 but 293:313), and Celsius or Fahrenheit inputs convert to kelvin automatically. Add Avogadro's insight about the amount of gas n and this law becomes the full ideal gas law, PV = nRT.

Worked example 6.4. Given P1P_1 = 1 atm, V1V_1 = 1 L, T1T_1 = 273.15 K, P2P_2 = 0.5 atm, T2T_2 = 546.3 K; find V2V_2 (final volume). 1 L at 1 atm, 273.15 K → 0.5 atm, 546.3 K gives 4 L.

(Chemistry 12-46)V=n VmV = n\,V_m
Where
  • VV= Gas volume at STP (L)
  • nn= Amount of gas (mol)
Vn
Figure 6.5: gas volume at stp.

Fix the temperature and pressure and a mole of any ideal gas occupies the same volume, so converting between moles and litres needs one constant and no information about the substance. This is Avogadro's principle, and it deserves a moment of surprise before it becomes routine. A mole of hydrogen weighs 2 g and a mole of sulfur hexafluoride weighs 146 g, seventy-three times more, yet at the same conditions they fill the same flask. The reason is that pressure comes from the number of impacts and their momentum, and at a common temperature the heavier molecules move proportionally slower. The mass cancels out of everything the container can feel.

This page uses classic STP, 0 °C and 1 atm, where Vm=22.414V_m = 22.414 L/mol. Burning one mole of methane, CH4+2O2→CO2+2H2O\text{CH}_4 + 2\text{O}_2 \rightarrow \text{CO}_2 + 2\text{H}_2\text{O}, consumes 2 mol of oxygen and produces 1 mol of carbon dioxide, which is 44.83 L of O₂ in and 22.41 L of CO₂ out at STP. Note that the two moles of water do not appear in that volume tally, because at 0 °C the water is a liquid and the equation only counts gases.

The constant is not independent; it is PV=nRTPV = nRT evaluated once. Vm=RT/P=(8.314×273.15)/101 325=0.022414V_m = RT/P = (8.314 \times 273.15)/101\,325 = 0.022414 m³/mol, and every other molar volume in circulation is the same calculation at different conditions. Historically the logic ran the other way. Gay-Lussac reported in 1808 that gases combine in simple whole-number volume ratios, two volumes of hydrogen to one of oxygen, and Avogadro's 1811 hypothesis explained why: equal volumes hold equal counts, so the volume ratios are the mole ratios of the balanced equation. That insight was ignored for half a century before Cannizzaro revived it at Karlsruhe in 1860.

The error that dominates this page is using 22.4 L/mol for conditions that are not STP. Room temperature is not 0 °C. At 25 °C and 1 atm the molar volume is 24.47 L/mol, so applying 22.4 to a bench-top measurement understates the volume by 9%. And "standard conditions" is not one definition but several: classic STP gives 22.414 L/mol, IUPAC's post-1982 STP (0 °C, 100 kPa) gives 22.711, and SATP (25 °C, 100 kPa) gives 24.79. The spread between the smallest and largest is over 10%, which is far more than the precision most people think they are carrying. Check which convention a source assumes before you borrow its number, and when the conditions are anything other than a listed standard, abandon the shortcut and use the ideal gas law directly.

Two smaller cautions. This is an ideal-gas result, so it degrades for gases near their condensation point: ammonia and sulfur dioxide at STP already deviate by a percent or two, and water vapour at 0 °C is not a gas at all. And when you use volume ratios as mole ratios in a reaction, they apply only to the species that are actually gaseous at the stated conditions. A dissolved or condensed product contributes no volume, and counting it is the quiet way to get a stoichiometry problem wrong.

Worked example 6.5. Given nn = 1 mol; find VV (gas volume at stp). 1 mol ideal gas at STP → 22.414 L.

(Chemistry 12-47)ρ=PMRT\rho = \frac{PM}{RT}
Where
  • ρ\rho= Gas density (kg/m³)
  • PP= Pressure (kPa)
  • MM= Molar mass (g/mol)
  • TT= Absolute temperature (°C)
PρMT
Figure 6.6: gas density from molar mass.

Start from PV=nRTPV = nRT, substitute n=m/Mn = m/M, and rearrange for mass over volume: ρ=PM/RT\rho = PM/RT. What the result says is that a gas has no density of its own. Unlike a solid or a liquid, whose density is close enough to a fixed property to tabulate, a gas takes whatever density its pressure and temperature impose, and the only thing the substance itself contributes is MM. Squeeze it and it gets denser in exact proportion; warm it and it thins in inverse proportion.

Air at 101.325 kPa and 20 °C, using M=0.028964M = 0.028964 kg/mol: ρ=(101 325×0.028964)/(8.314×293.15)=1.204 kg/m3\rho = (101\,325 \times 0.028964)/(8.314 \times 293.15) = 1.204\ \text{kg/m}^3, the figure every ventilation calculation starts from. Helium at the same conditions, with M=0.0040026M = 0.0040026, comes to 0.166 kg/m³. Subtract, and a cubic metre of helium lifts about 1.04 kg. That is the entire physics of a party balloon, and it explains why a balloon large enough to lift a person has to be the size of a house.

Rearranged for molar mass the equation becomes a measurement rather than a prediction, and a historically important one. Weigh a bulb of known volume empty, fill it with a vapour at measured temperature and pressure, weigh it again, and M=ρRT/PM = \rho RT/P hands you the molar mass of an unknown. This is the Dumas method, and through the middle of the nineteenth century it was one of the few routes to a molecular formula. It also settled arguments: measured vapour densities are what showed that many elemental gases travel as diatomic molecules rather than lone atoms.

The dominant error here is the molar mass unit, and it is a clean factor of a thousand. With R=8.314R = 8.314 J/(mol·K) the equation demands MM in kilograms per mole. Air is 0.029 kg/mol. Enter 29 and the answer comes back as 1204 kg/m³, air denser than water, which at least announces itself. Enter 0.029 when the calculation wanted grams and you get the mirror error. The usual companions apply too: PP must be absolute, not a gauge reading, and TT must be in kelvin.

Two conceptual notes. There is no such thing as "the molar mass of air" in the strict sense: air is a mixture, and 28.96 g/mol is a mole-weighted average of nitrogen, oxygen and argon. It works precisely because an ideal gas is indifferent to what its neighbours are; only the total count matters. That same indifference produces a result most people find backwards: humid air is lighter than dry air. Water is 18 g/mol against air's 29, so at a given pressure and temperature every water molecule that joins the mixture has displaced a heavier one. Muggy days are low-density days, which is why aircraft performance charts include humidity and why a hot, humid runway is a long takeoff.

Worked example 6.6. Given PP = 1 atm, MM = 32.00 g/mol, TT = 273.15 K; find ρ\rho (gas density). O2 at STP (1 atm, 273.15 K) → 1.42768 kg/m3.

(Chemistry 12-48)Pi=xi PtotalP_i = x_i \, P_{\text{total}}
Where
  • PiP_i= Partial pressure of component i (kPa)
  • xix_i= Mole fraction of component i
  • PtotalP_{\text{total}}= Total pressure (kPa)
PtotalxiPi
Figure 6.7: partial pressure from mole fraction.

John Dalton realised in 1801 that gas molecules in a mixture ignore one another: each exerts the pressure it would exert alone, and the total is their sum. Divide through by the total and you get the form everyone actually uses: a component's partial pressure is its mole fraction times the total pressure. Dry air is 20.9% oxygen by mole, so at 101.325 kPa the oxygen partial pressure is 0.209 × 101.325 = 21.2 kPa, and that number, not the percentage, is what drives oxygen across the alveolar membrane.

This is why altitude matters and composition does not: the air on top of Everest is still 20.9% oxygen, but at 33 kPa total pressure the oxygen partial pressure falls to about 7 kPa, roughly a third of sea-level value. Divers meet the same arithmetic in reverse: at 40 m the ambient pressure is 5 atm, so ordinary air delivers an oxygen partial pressure above 1 atm and a nitrogen partial pressure near 4 atm, which is where oxygen toxicity and nitrogen narcosis begin. The trap is mixing up mole fraction with mass fraction or volume percent; only mole fraction goes into this equation, though for ideal gases volume percent happens to equal it.

Worked example 6.7. Given xix_i = 0.209, PtotalP_{\text{total}} = 1.00 atm; find PiP_i (partial pressure of component i). O2 in air: x = 0.209 at 1.00 atm → 21.177 kPa.

(Chemistry 12-49)x1=n1n1+n2x_1 = \frac{n_1}{n_1 + n_2}
Where
  • x1x_1= Mole fraction of solute
  • n1n_1= Amount of solute (mol)
  • n2n_2= Amount of solvent (mol)
n1n2x1
Figure 6.8: mole fraction.

The mole fraction asks the simplest possible concentration question: of every mole of particles in the mixture, what share belongs to component 1? Dissolve 1.00 mol of ethylene glycol in 9.00 mol of water and x₁ = 1.00/(1.00 + 9.00) = 0.100: no units, no temperature dependence, and all the mole fractions in a mixture always sum to exactly 1.

This makes x the natural currency of vapor-pressure laws: Raoult's law and Dalton's law are both written in mole fractions, and gas mixtures are routinely quoted this way. Dry air is x ≈ 0.78 nitrogen and 0.21 oxygen. Solving the definition backwards for n₁ or n₂ requires x strictly between 0 and 1, since a pure component (x = 1) carries no information about how much solvent could be present.

Worked example 6.8. Given n1n_1 = 1 mol, n2n_2 = 9 mol; find x1x_1 (mole fraction of solute). 1 mol solute + 9 mol solvent → x1 = 0.1.

(Chemistry 12-50)r1r2=M2M1\frac{r_1}{r_2} = \sqrt{\frac{M_2}{M_1}}
Where
  • r1r_1= Effusion rate of gas 1 (L/min)
  • r2r_2= Effusion rate of gas 2 (L/min)
  • M1M_1= Molar mass of gas 1 (g/mol)
  • M2M_2= Molar mass of gas 2 (g/mol)
r1r2M1M2
Figure 6.9: graham's law of effusion.

Temperature is a measure of average kinetic energy, and at a given temperature every gas in the room has the same average 12mv2\tfrac{1}{2}mv^2 per molecule. If the energies match and the masses do not, the speeds must compensate: v∝1/mv \propto 1/\sqrt{m}. A molecule that finds a pinhole does so at a rate set by how fast it is travelling, so the escape rates of two gases stand in the inverse ratio of the square roots of their molar masses. The square root is the whole content of the law, and it comes from the square in the kinetic energy.

Helium against nitrogen: 28.01/4.003=6.997=2.65\sqrt{28.01/4.003} = \sqrt{6.997} = 2.65. Helium leaves 2.65 times faster, which is why a helium balloon is limp by morning while an air-filled one holds for weeks. Note that a factor of seven in mass buys only a factor of 2.65 in rate: the square root flattens everything, and that flattening has consequences.

Thomas Graham established the relation in 1848 by timing gases through a plaster plug. Its most consequential application came a century later. Uranium enrichment needs to separate ²³⁵U from ²³⁸U, and the only usable gaseous compound is uranium hexafluoride: 349.03 g/mol against 352.04. The separation factor is 352.04/349.03=1.0043\sqrt{352.04/349.03} = 1.0043: four-tenths of one percent per stage. To go from natural uranium to reactor grade takes over a thousand stages in cascade, and the K-25 plant built at Oak Ridge to do it enclosed some seventeen hectares under one roof and was for a time the largest building in the world. The square root is the reason it had to be that big.

Effusion is not diffusion, and Graham's law is a law about effusion. Effusion is escape through an opening small compared with the mean free path, so molecules leave one at a time without colliding on the way out: a pure speed contest. Diffusion is one gas spreading through another, and it is dominated by collisions, not by free flight. Graham's law describes diffusion only roughly, and the approximation degrades as pressure rises and collisions multiply. A leak through a crack in a fitting is usually closer to fluid flow than to either.

Two arithmetic traps. The subscripts are deliberately crossed, r1/r2=M2/M1r_1/r_2 = \sqrt{M_2/M_1}, with 2 over 1 on the right, and inverting them is the commonest slip on this page. The sanity check is free: the lighter gas must always come out faster, so if your answer says otherwise, flip it. The second is confusing rate with time. If helium effuses 2.65 times faster, it takes 1/2.65=0.3771/2.65 = 0.377 times as long to release the same quantity. Rates and times are reciprocals, and a question worded "how long" wants the reciprocal of a question worded "how fast". Both gases must also be at the same temperature and pressure for the comparison to mean anything.

Worked example 6.9. Given r2r_2 = 1.00 L/min, M1M_1 = 2.016 g/mol, M2M_2 = 32.00 g/mol; find r1r_1 (effusion rate of gas 1). H2 vs O2: r1 = sqrt(32.00/2.016) = 3.98410 L/min.

(Chemistry 12-51)b=nmsolventb = \frac{n}{m_{\text{solvent}}}
Where
  • bb= Molality (mol/kg)
  • nn= Amount of solute (mol)
  • msolventm_{\text{solvent}}= Mass of solvent (kg)
msolventnb
Figure 6.10: molality (b = n/m).

Molality looks like molarity's twin but divides by the mass of solvent, not the volume of solution, and that swap is the whole point. Dissolve 0.500 mol of glucose in 250 g (0.250 kg) of water and the molality is 0.500/0.250 = 2.00 mol/kg, a value that stays exactly 2.00 whether the flask sits in an ice bath or on a hot plate, because mass does not expand with temperature the way volume does.

That temperature-independence is why colligative-property formulas, boiling-point elevation and freezing-point depression, are written in terms of molality. For dilute aqueous solutions the two scales nearly coincide (1 L of water is 1 kg), but in concentrated solutions or non-aqueous solvents they diverge sharply, and mixing them up is a classic exam trap.

Worked example 6.10. Given nn = 0.5 mol, msolventm_{\text{solvent}} = 250 g; find bb (molality). 0.5 mol in 250 g water → b = 2 mol/kg.

(Chemistry 12-52)c=msolutemsolution×100%c = \frac{m_{\text{solute}}}{m_{\text{solution}}} \times 100\%
Where
  • cc= Mass percent (%)
  • msolutem_{\text{solute}}= Mass of solute (kg)
  • msolutionm_{\text{solution}}= Mass of solution (kg)
msolutemsolutionc
Figure 6.11: mass percent of a solution.

Mass percent is the concentration measure that needs nothing but a balance: the solute's mass divided by the mass of the whole solution, solute plus solvent, times 100. Dissolve 25 g of salt in 225 g of water and the solution is 25/250 × 100 = 10% salt by mass. The classic mistake is dividing by the solvent mass alone, which would wrongly give 11.1%.

Because it is temperature-proof and instrument-free, mass percent dominates industrial and household labels: household vinegar is about 5% acetic acid, physiological saline 0.9% NaCl, seawater roughly 3.5% dissolved salts, and concentrated sulfuric acid ships at 98%. Converting to molarity requires the solution's density, which is why bottle labels for concentrated acids list both figures side by side.

Worked example 6.11. Given msolutem_{\text{solute}} = 25 g, msolutionm_{\text{solution}} = 250 g; find cc (mass percent). 25 g salt in 250 g solution → c = 10%.

(Chemistry 12-53)ΔTb=Kb b\Delta T_b = K_b \, b
Where
  • ΔTb\Delta T_b= Boiling-point elevation (C°)
  • KbK_b= Ebullioscopic constant (K·kg/mol)
  • bb= Molality of solution (mol/kg)
ΔTbKbb
Figure 6.12: boiling-point elevation.

A non-volatile solute lowers the solvent's vapor pressure, so the solution must be heated a little hotter before that pressure reaches the atmosphere's: the boiling point rises. The rise depends only on how many particles are dissolved, not what they are, scaled by the solvent's ebullioscopic constant Kb. Water's Kb is a modest 0.512 K·kg/mol: a hearty 1.0 mol/kg sugar solution boils at just 100.5 °C, which is why salting pasta water changes its flavor far more than its physics.

Other solvents respond much more strongly (benzene's Kb is 2.53 and camphor's freezing-side cousin is famously huge) and remember that ionic solutes count each ion: 1 mol/kg NaCl acts as nearly 2 mol/kg of particles. Solved backwards, a measured ΔTb divided by Kb gives the molality, the classical route to a dissolved compound's molar mass before mass spectrometers existed.

Worked example 6.12. Given KbK_b = 0.512 K·kg/mol, bb = 1 mol/kg; find ΔTb\Delta T_b (boiling-point elevation). Kb = 0.512, b = 1 mol/kg → dT = 0.512 K.

(Chemistry 12-54)ΔTf=Kf b\Delta T_f = K_f \, b
Where
  • ΔTf\Delta T_f= Freezing-point depression (C°)
  • KfK_f= Cryoscopic constant (K·kg/mol)
  • bb= Molality of solution (mol/kg)
ΔTfKfb
Figure 6.13: freezing-point depression.

Dissolved particles get in the way of solvent molecules trying to organize into a crystal, so the solution must be cooled below the pure solvent's freezing point before ice can form. The depression ΔTf is proportional to molality through the cryoscopic constant Kf: for water, 1.86 K·kg/mol, more than three times its boiling-side constant. A 2.0 mol/kg ethylene glycol solution freezes at −3.7 °C, and a fully protected automotive antifreeze mix pushes well below −30 °C by the same mechanism.

The effect is everywhere: road salt melts ice because brine freezes lower than pure water (each mole of CaCl₂ delivers three moles of particles), and hand-cranked ice cream relies on a salt–ice bath dropping below −10 °C. In the lab, camphor's giant Kf of about 40 K·kg/mol made the "Rast method" possible: weighing a solute into molten camphor and reading its molar mass off a melting-point depression measured with an ordinary thermometer.

Worked example 6.13. Given KfK_f = 1.86 K·kg/mol, bb = 2 mol/kg; find ΔTf\Delta T_f (freezing-point depression). Kf = 1.86, b = 2 mol/kg → dT = 3.72 K.

(Chemistry 12-55)Π=MRT\Pi = M R T
Where
  • Π\Pi= Osmotic pressure (kPa)
  • MM= Molar concentration (M)
  • TT= Absolute temperature (°C)
ΠMT
Figure 6.14: osmotic pressure (π = mrt).

Separate a solution from pure water by a membrane that passes only water, and water flows in until the extra hydrostatic pressure, the osmotic pressure Π, stops it. Van 't Hoff noticed that dilute solutes behave like an ideal gas trapped in the solution, so Π = MRT with the same gas constant, R = 8.314 J/(mol·K). Physiological saline (0.154 M NaCl, which dissociates into about 0.308 mol/L of particles) at body temperature gives Π = 308 mol/m³ × 8.314 × 310 K ≈ 7.9 × 10⁵ Pa: roughly 7.7 atm, which is why IV fluids must match blood's osmolarity or red cells swell and burst.

The effect is enormous per mole: even a 0.010 M sugar solution at 25 °C pushes with about 0.24 atm, equivalent to a 2.5 m column of water. That sensitivity makes osmotic pressure the classic method for measuring the molar mass of polymers and proteins, where a tiny molar concentration of huge molecules still produces a comfortably measurable pressure. Reverse osmosis simply runs the equation backwards: seawater's ~27 atm of osmotic pressure sets the minimum pressure a desalination pump must beat.

Worked example 6.14. Given MM = 0.1 M, TT = 298.15 K; find Π\Pi (osmotic pressure). 0.1 M at 298.15 K → Pi = 247.8957 kPa.

(Chemistry 12-56)P=x P0P = x \, P^{0}
Where
  • PP= Vapour pressure over solution (kPa)
  • xx= Mole fraction of solvent
  • P0P^{0}= Vapour pressure of pure solvent (kPa)
P0Px
Figure 6.15: raoult's law.

Molecules can only evaporate from the liquid's surface, and dissolving a non-volatile solute means some of that surface is occupied by particles that cannot leave. François-Marie Raoult found in the 1880s that the effect is exactly proportional: the solvent's vapor pressure drops to its mole fraction times the pure-solvent value. Pure water at 25 °C exerts 3.17 kPa; a solution where water's mole fraction is 0.90 (say, 1 mol of glucose per 9 mol of water) exerts P = 0.90 × 3.17 = 2.85 kPa.

This vapor-pressure lowering is the root of all colligative properties: boiling-point elevation and freezing-point depression both follow from it. Real solutions obey Raoult's law best when dilute and when solute–solvent interactions resemble solvent–solvent ones; strong deviations from the straight line are the chemist's first diagnostic that a mixture is far from ideal, like the ethanol–water pair that refuses to distill past 95%.

Worked example 6.15. Given xx = 0.9, P0P^{0} = 3.17 kPa; find PP (vapour pressure over solution). x = 0.90, P0 = 3.17 kPa → P = 2.853 kPa.

(Chemistry 12-57)C=H PC = H\,P
Where
  • CC= Dissolved concentration (mol/m³)
  • HH= Henry solubility constant (mol/(m³·Pa))
  • PP= Partial pressure (kPa)
PCH
Figure 6.16: henry's law (gas solubility).

William Henry found in 1803 that a gas dissolves in proportion to its partial pressure above the liquid, and the constant of proportionality is the one number a whole field of environmental engineering rests on. Oxygen at 25 °C has Hcp=1.3×10−5H^{cp} = 1.3\times 10^{-5} mol/(m³·Pa). Air puts 21% of an atmosphere of oxygen over a lake, which is 21278 Pa, so the water holds 1.3×10−5×21278=0.2771.3\times 10^{-5}\times 21278 = 0.277 mol/m³, or about 8.9 mg/L once you multiply by 32 g/mol. That is the dissolved oxygen reading a probe gives in air-saturated water, and the number every aeration system is designed against.

The units are a minefield, and it is worth being blunt about it. There are at least five conventions in circulation: solubility forms with concentration over pressure, volatility forms with pressure over concentration, dimensionless air-water partition coefficients, and versions using mole fraction instead of concentration. They are reciprocals and rescalings of one another, so getting one wrong produces an answer off by many orders of magnitude. This page uses the solubility form HcpH^{cp} in mol/(m³·Pa), which is the convention Sander's compilation tabulates.

Two things the equation does not say out loud. Solubility falls sharply with temperature, roughly halving between 0 and 30 °C for oxygen, which is why summer fish kills happen in warm shallow water exactly when the fish need oxygen most. And Henry's law is a dilute-solution law: it describes the solute, while Raoult's law describes the solvent, and the two are the opposite limits of the same curve. Push the concentration up towards saturation and the linear relation quietly stops being true.

Worked example 6.16. Given HH = 1.3e-5, PP = 21278.25 Pa; find CC (dissolved concentration). Air-saturated water at 25 degC holds 0.2766 mol/m3 of O2.

6.17 Clausius–Clapeyron Equation (Two-Point Form)

Solve it online →formula.expert/solvers/clausius-clapeyron-two-point
(Chemistry 12-58)ln⁡ ⁣(P2P1)=−ΔHvapR(1T2−1T1)\ln\!\left(\frac{P_2}{P_1}\right) = -\frac{\Delta H_{vap}}{R}\left(\frac{1}{T_2} - \frac{1}{T_1}\right)
Where
  • P1P_1= Vapour pressure at T₁ (kPa)
  • T1T_1= Temperature 1 (°C)
  • P2P_2= Vapour pressure at T₂ (kPa)
  • T2T_2= Temperature 2 (°C)
  • ΔHvap\Delta H_{vap}= Enthalpy of vaporisation (kJ/mol)
T1P1T2P2ΔH
Figure 6.17: clausius–clapeyron equation (two-point form).

Integrate the Clapeyron equation with the two honest simplifications, that the vapour is ideal and that ΔHvap\Delta H_{vap} does not change over the interval, and this two-point form falls out. It is the workhorse for turning two boiling points into an enthalpy of vaporisation, or one boiling point into all the others. A liquid boiling at 373.15 K under one atmosphere and at 354.75 K under half an atmosphere has ΔHvap=Rln⁡2/(1/354.75−1/373.15)=41.5 kJ/mol\Delta H_{vap} = R\ln 2 / (1/354.75 - 1/373.15) = 41.5\ \text{kJ/mol}, which is water to within a couple of percent.

Run it forward on water from 100 °C down to 80 °C with ΔHvap=40.7 kJ/mol\Delta H_{vap} = 40.7\ \text{kJ/mol} and it predicts 48.2 kPa. Steam tables say 47.4 kPa. That 1.7% gap is not an arithmetic error, it is the cost of holding ΔH\Delta H constant across 20 K, and it grows fast as you widen the interval. Near the critical point ΔHvap\Delta H_{vap} collapses towards zero and the equation fails outright.

The unglamorous mistake is temperature units. Both temperatures go in as absolute values, because they appear as 1/T1/T and the reciprocal of a Celsius reading is meaningless. This page takes any temperature unit and converts, but if you are working the equation on paper, convert to kelvin first. The unexpected use, incidentally, is in the kitchen and on mountains: the same equation, run backwards, tells you that at 3000 m water boils near 90 °C, which is why high-altitude cooking directions exist.

Worked example 6.17. Given P1P_1 = 101.325 kPa, T1T_1 = 100 °C, T2T_2 = 80 °C, ΔHvap\Delta H_{vap} = 40.7 kJ/mol; find P2P_2 (vapour pressure at t₂). Water at 80 degC → 48.20 kPa from the 100 degC point.

Module 6 practice

65. Combined and ideal: A piston cylinder traps 10.0 L of an ideal gas at 120 kPa and 27 °C. The piston is driven in until the gas fills 5.0 L, and by then the gas has reached 77 °C. Calculate the pressure of the gas in its final state.

66. Combined and ideal: A fixed sample of an ideal gas starts at 150 kPa, 8.0 L and 27 °C. After a run through the plant it is found at 100 kPa in a 6.0 L receiver. Determine the sample's final absolute temperature, in kelvin.

67. Molar mass from the gas: An unlabelled cylinder in the prep room is vented into an evacuated bulb of known volume. The gas inside behaves ideally, and at 150 kPa and 77 °C a litre of it weighs 2.371 g. On this paper R = 8.314 kPa·L/(mol·K). Determine the gas's molar mass, then identify the gas.

68. Molar mass from the gas: An unlabelled cylinder in the prep room is vented into an evacuated bulb of known volume. The gas inside behaves ideally, and at 100 kPa and 47 °C a litre of it weighs 0.752 g. On this paper R = 8.314 kPa·L/(mol·K). Determine the gas's molar mass, then identify the gas.

69. Partial pressures: A rigid vessel holds 2.0 mol of oxygen and 3.0 mol of helium. The mixture reads 300 kPa on the vessel's gauge, and both gases behave ideally. Calculate the partial pressure of the oxygen.

70. Partial pressures: A gas header runs at a total pressure of 300 kPa and carries 6.0 mol of gas in all. A probe reports that the argon in the header exerts 225 kPa. Determine the amount of argon in the header.

71. Graham's race: Two identical vessels, one of He (4 g/mol) and one of CH₄ (16 g/mol), are held at the same temperature and pressure. Each is pierced with an identical pinhole and the gases are allowed to effuse. Determine how many times faster He effuses than CH₄.

72. Graham's race: Through one pinhole, CH₄ (16 g/mol) effuses at 48 mL/s. The same apparatus at the same temperature and pressure is then filled with SO₂ (64 g/mol). Calculate the effusion rate of the SO₂.

73. Three ways to say how much: A technician weighs 101 g of potassium nitrate (M = 101 g/mol), dissolves it, and makes the solution up to 250 mL in a volumetric flask. Calculate the molar concentration of the solution.

74. Three ways to say how much: A 0.5 mol sample of a non-volatile solute is stirred into 250 g of water. The solution is not made up to any particular volume — the water was simply weighed out first. Calculate the molality of the solution.

75. Colligative counting: A 0.5 mol/kg solution of a non-volatile, non-ionizing solute in water is cooled in a jacket. For water Kf = 1.86 °C·kg/mol, and pure water freezes at 0 °C. Determine the temperature at which this solution begins to freeze.

76. Colligative counting: A 1 mol/kg solution of a non-volatile, non-ionizing solute in water is heated on a hotplate at standard atmospheric pressure. For water Kb = 0.512 °C·kg/mol, and pure water boils at 100 °C. Determine the temperature at which this solution boils.

77. Vapour pressure stories: A solution is prepared from 3.0 mol of a non-volatile solute and 7.0 mol of a solvent whose pure vapour pressure at this temperature is 80 kPa. The mixture behaves ideally. Calculate the vapour pressure of the solvent above the solution.

78. Vapour pressure stories: Above an ideal solution whose solvent mole fraction is 0.6, a manometer reads a solvent vapour pressure of 36 kPa at the working temperature. Determine the vapour pressure of the pure solvent at that temperature.

79. The Gas Works: Last batch of the shift. The gas works draws 4.0 mol of carbon dioxide (44 g/mol) from the reservoir at STP — 101 kPa, 273 K, molar volume 22.4 L/mol. The compressor delivers it to the kiln line at 404 kPa and 819 K. Downstream the batch is blended into a header that carries 4 mol of nitrogen for every mole of the batch gas, and the header runs at 800 kPa in total. Work each line — every answer feeds the next. Determine, line by line, what the batch does on its way through the works.

80. The Gas Works: Bonus mark, and still no calculator. An unmarked cylinder is found behind the compressor house. Vented into a bulb at STP, its gas weighs 0.714 g per litre. At STP one mole of any ideal gas fills 22.4 L. Determine the gas's molar mass, and name the gas.

Answer key

  1. 20,900 J
  2. -10,450 J
  3. 6,680 J
  4. 10,450 J
  5. -1,452 kJ
  6. -2,734 kJ
  7. 3,009.6 J
  8. 20,064 J
  9. 51 kJ/mol
  10. 226 kJ/mol
  11. -1,029 kJ/mol
  12. -792 kJ/mol
  13. 0.25 mol
  14. 1,600 kJ/mol
  15. 3,575 s⁻¹
  16. 3,575 s⁻¹
  17. 53.5973 kJ/mol
  18. 41.5723 kJ/mol
  19. 0.9 mol/L
  20. 0.200059 mol/L
  21. 11.9922 s
  22. 0.0693147 s⁻¹
  23. 0.04 mol/L
  24. 50 s
  25. 0.01 s⁻¹
  26. 9 ×
  27. 8 (no unit)
  28. 3 (no unit)
  29. 5 (no unit)
  30. 2.5 (no unit)
  31. 2 (no unit)
  32. 123.086 (no unit)
  33. 0.0002 mol/L
  34. 0 (mol/L)³
  35. 4.552 kJ/mol
  36. 750 K
  37. 100 (no unit)
  38. 100 (no unit)
  39. 3 (no unit)
  40. 4.09691 (no unit)
  41. 9 (no unit)
  42. 0.00000125 (no unit)
  43. 3.69897 (no unit)
  44. 2 %
  45. 7.2 (no unit)
  46. 6.79309 (no unit)
  47. 0.5 L
  48. 0.3 mol/L
  49. 0.06 mol/L
  50. 0.003 mol
  51. 0.02 mol/L
  52. 4 (no unit)
  53. -0.45 V
  54. -0.26 V
  55. 1.1488 V
  56. 1.1296 V
  57. 5,400 C
  58. 57,600 C
  59. 0.6 mol e⁻
  60. 0.2 mol e⁻
  61. 19.3 A
  62. 9.53 g
  63. -1.49 V
  64. 2 e⁻ per ion
  65. 280 kPa
  66. 150 K
  67. 45.9958 g/mol
  68. 20.0068 g/mol
  69. 0.4 (no unit)
  70. 0.75 (no unit)
  71. 2 ×
  72. 24 mL/s
  73. 4 mol/L
  74. 2 mol/kg
  75. 0.93 C°
  76. 0.512 C°
  77. 0.7 (no unit)
  78. 60 kPa
  79. 89.6 L
  80. 15.9936 g/mol