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Unit 7: Equilibrium

AP Chem cheatsheet

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Most reactions we have looked at previously were irreversible reactions, or reactions that can only go one way (forward). A reversible reaction can run in both directions (forward and backwards). In a closed system (no escape of matter), the forward reaction consumes reactants and forms products, while the reverse reaction does the opposite. Chemical equilibrium is reached when the rate of the forward reaction equals the rate of the reverse reaction. At that point:

  • Concentrations (or for gases, partial pressures) remain constant over time (they are not necessarily equal to one another)
  • The system is dynamic: molecules still react, but there is no net change in amounts. This is different from a completed or irreversible reaction, where at least one reactant is effectively exhausted and the process does not establish a lasting balance between forward and reverse paths at ordinary conditions.

The approach to equilibrium has a characteristic shape: starting from pure reactants, the forward rate is high (reactant concentrations are large) and the reverse rate is zero. As products build up, the forward rate falls and the reverse rate rises until the two are equalβ€”from that moment on, concentrations level off and stay flat. Crucially, β€œequal rates” does not mean β€œequal concentrations”; the leveled-off amounts can be lopsided in either direction depending on KK.

reactantsproductstimeconcentrationequalratestimerate

Homogeneous equilibrium means all reacting species are in the same phase (e.g. all gases, or all in one solution). Heterogeneous equilibrium includes pure solids or pure liquids as separate phases; their activities are taken as constant and they are omitted from the equilibrium expression (see below).

Example. In a sealed vessel at equilibrium, product concentration is twice reactant concentration. A student says the reverse rate must therefore be twice the forward rate. Evaluate the claim.

Equilibrium requires equal forward and reverse rates, not equal concentrations. Different rate constants and concentration dependences allow unequal amounts while the two rates balance. Constant measured concentrations establish no net change; they do not imply that molecular reactions have stopped.


For a balanced reaction in solution (molar concentrations in mol/L\text{mol/L}),

jA+kBβ‡ŒlC+mD,j\text{A} + k\text{B} \rightleftharpoons l\text{C} + m\text{D},

the equilibrium constant in terms of concentration is

Kc=[C]l[D]m[A]j[B]k,K_c = \frac{[\text{C}]^l [\text{D}]^m}{[\text{A}]^j [\text{B}]^k},

where each [][] is the equilibrium molarity raised to the power of the stoichiometric coefficient. Only aqueous solutes or gases appear in KcK_c, since the concentrations of pure solids/liquids do not change, and therefore are always assumed to be 1. In addition, KcK_c will not change unless temperature changes, so KcK_c is only temperature-dependent.

On the AP exam, KK is treated as a dimensionless ratio by implicitly comparing each concentration to a standard reference (standard state). Regardless, you should still use the same algebraic form when you set up problems.

Orders of magnitude help you judge extent (at a given temperature):

  • If KcK_c is very large (e.g. Kc≫1K_c \gg 1, sometimes textbook thresholds like Kc>1010K_c > 10^{10}), the forward reaction is product-favored at equilibriumβ€”substantial conversion to products. This usually means that the forward reaction is approximately an irreversible reaction
  • If KcK_c is very small (e.g. Kcβ‰ͺ1K_c \ll 1, sometimes Kc<10βˆ’10K_c < 10^{-10}), the mixture stays reactant-heavy, meaning that the reaction basically did not start at all.

These cutoffs are rules of thumb; what matters is comparing QQ to KK and interpreting KK relative to 11.

Example. A reaction has Kc=1012K_c=10^{12} but produces no detectable product during a short observation. Must either the measurement or the equilibrium constant be wrong?

No. The large constant predicts a product-favored equilibrium composition, not the time needed to reach it. A large activation barrier can make the forward rate extremely small. A catalyst could help the mixture approach equilibrium faster without changing KcK_c. Thermodynamic preference and observable reaction speed answer different questions.

  • Reverse reaction: Kc,reverse=1Kc,forward.K_{c,\text{reverse}} = \frac{1}{K_{c,\text{forward}}}.
  • Multiply the whole equation by an integer nn: Kcβ€²=(Kc)nK_c' = (K_c)^n
  • Add sequential steps (all at the same temperature): the overall KK is the product of the step constants: Koverall=K1Γ—K2Γ—β‹―K_{\text{overall}} = K_1 \times K_2 \times \cdots

Example. For Aβ‡Œ2BA\rightleftharpoons2B, K=9K=9. Find K for Bβ‡Œ12AB\rightleftharpoons\tfrac12 A and explain why taking only the reciprocal is insufficient.

Reversing gives 2Bβ‡ŒA2B\rightleftharpoons A with constant 1/91/9. Dividing all coefficients by two takes its square root, giving Kβ€²=1/3K'=1/3. The equilibrium expression has both its numerator/denominator and its exponents changed.


For gas-phase equilibria it is often convenient to use partial pressures (in atmospheres on the AP exam, unless stated otherwise). For

jA(g)+kB(g)β‡ŒlC(g)+mD(g),j\text{A}(g) + k\text{B}(g) \rightleftharpoons l\text{C}(g) + m\text{D}(g),

define

Kp=(PC)l(PD)m(PA)j(PB)k.K_p = \frac{(P_{\text{C}})^l (P_{\text{D}})^m}{(P_{\text{A}})^j (P_{\text{B}})^k}.

Only gaseous species appear (since aqueous solutions and pure solids/liquids do not have partial pressures). From the ideal gas law, P=(n/V)RT=MRTP = (\text{n/V})RT = MRT for a gas (M = molarity). The standard relationship is

Kp=Kc(RT)Ξ”ngas,K_p = K_c (RT)^{\Delta n_{\text{gas}}},

where Ξ”ngas\Delta n_{\text{gas}} is difference between the amount of moles of products and reactants (from the balanced equation), and RR must be consistent with the pressure units used (e.g. R=0.0821Β Lβ‹…atm/(molβ‹…K)R = 0.0821\ \text{LΒ·atm/(molΒ·K)} when PP is in atm).

Example. For N2O4(g)β‡Œ2NO2(g)\mathrm{N_2O_4(g)\rightleftharpoons2NO_2(g)}, a student sets Kp=KcK_p=K_c because all species are gases. Identify the missing factor.

The change in gas mole coefficients is Ξ”n=2βˆ’1=1\Delta n=2-1=1. With the usual textbook unit convention, Kp=Kc(RT)K_p=K_c(RT). Equality would follow for Ξ”n=0\Delta n=0, not merely from all species being gaseous. Temperature must be expressed in kelvin and R must match pressure units.


The reaction quotient has the same algebraic form as KK, but it uses concentrations or pressures at any instant, not necessarily at equilibrium.

For concentrations:

Qc=[C]l[D]m[A]j[B]k.Q_c = \frac{[\text{C}]^l [\text{D}]^m}{[\text{A}]^j [\text{B}]^k}.
  • If Q<KQ < K, the ratio of products to reactants is too small for equilibrium; the system shifts right (toward products).
  • If Q>KQ > K, the ratio is too large; the system shifts left (toward reactants).
  • If Q=KQ = K, the system is at equilibrium.

A useful trick is to line up KK and QQ alphabetically (so KK on the left and QQ on the right), and whatever direction the sign goes (e.g. < (less than) goes left) is the direction the reaction goes.

The same logic applies to QpQ_p and KpK_p for gases.

QQ=KQ<KshiftrighttowardproductsQ>Kshiftlefttowardreactants

A catalyst speeds both forward and reverse rates equally, so it does not change KK or the equilibrium position - it only shortens the time needed to reach equilibrium.

Example. For Aβ‡Œ2BA\rightleftharpoons2B, an equilibrium mixture is suddenly compressed to half its volume at fixed temperature. Compare the new Q with K before any reaction occurs.

Both concentrations double, so Qβ€²=(2[B])22[A]=2KQ'=\frac{(2[B])^2}{2[A]}=2K. The reverse reaction is favored, reducing B and forming A. Tracking the concentration powers explains the shift without assuming that every compression favors reactants.


The link between standard Gibbs free energy change and the equilibrium constant (same temperature) is

Ξ”G∘=βˆ’RTln⁑K,\Delta G^\circ = -RT \ln K,

where KK is KcK_c or KpK_p according to how the reaction is expressed, and must match the standard-state convention your course uses. For many AP problems, KK is KcK_c for solution chemistry and KpK_p when all species are gases and the expression is written in pressures. The Gibbs free energy value determines if a reaction is spontaneous, which is talked about more in Unit 9.

Qualitative connections (at standard conditions, using KK relative to 11):

  • If K>1K > 1, then Ξ”G∘<0\Delta G^\circ < 0: the forward reaction is thermodynamically favorable (spontaneous) under standard conditions.
  • If K<1K < 1, then Ξ”G∘>0\Delta G^\circ > 0: the reverse direction is favored under standard conditions and the forward reaction is not spontaneous.
  • If K=1K = 1, then Ξ”G∘=0\Delta G^\circ = 0, meaning the reaction is at equilibrium.

For nonstandard conditions, the reaction quotient enters:

Ξ”G=Ξ”G∘+RTln⁑Q.\Delta G = \Delta G^\circ + RT \ln Q.

At equilibrium, Q=KQ = K and Ξ”G=0\Delta G = 0, which recovers Ξ”G∘=βˆ’RTln⁑K\Delta G^\circ = -RT \ln K. Here RR is the gas constant (8.314Β J/(molβ‹…K)8.314\ \text{J/(molΒ·K)} when using joules), and TT is kelvin.

Le ChΓ’telier’s principle says that KK changes with temperature only, and the van’t Hoff equation makes that dependence quantitative. It follows from the way Ξ”G∘=βˆ’RTln⁑K\Delta G^\circ = -RT\ln K combines with Ξ”G∘=Ξ”Hβˆ˜βˆ’TΞ”S∘\Delta G^\circ = \Delta H^\circ - T\Delta S^\circ when you ask how KK must move if TT changes (treating Ξ”H∘\Delta H^\circ and Ξ”S∘\Delta S^\circ as approximately constant over a modest temperature range: a standard AP assumption unless a problem says otherwise).

If K1K_1 and K2K_2 are equilibrium constants (same kind: both KcK_c or both KpK_p, matching how the reaction is written) at absolute temperatures T1T_1 and T2T_2, then

ln⁑K2K1=βˆ’Ξ”H∘R(1T2βˆ’1T1)=Ξ”H∘R(1T1βˆ’1T2).\ln\frac{K_2}{K_1} = -\frac{\Delta H^\circ}{R}\left(\frac{1}{T_2}-\frac{1}{T_1}\right) = \frac{\Delta H^\circ}{R}\left(\frac{1}{T_1}-\frac{1}{T_2}\right).

Here Ξ”H∘\Delta H^\circ is the standard enthalpy change for the reaction as written (see Unit 6: Thermochemistry). Use R=8.314Β J/(molβ‹…K)R = 8.314\ \text{J/(molΒ·K)} when Ξ”H∘\Delta H^\circ is in joules per mole of reaction as written.

Sign check: if the forward reaction is endothermic (Ξ”H∘>0\Delta H^\circ > 0) and T2>T1T_2 > T_1, then K2>K1K_2 > K_1β€”warming increases KK, matching the picture that heat acts like a reactant in an endothermic forward process. If the forward reaction is exothermic (Ξ”H∘<0\Delta H^\circ < 0), raising TT decreases KK.

The differential form (useful conceptually and in derivations) is

dln⁑KdT=Ξ”H∘RT2,\frac{d\ln K}{dT} = \frac{\Delta H^\circ}{RT^2},

which shows that sensitivity of ln⁑K\ln K to temperature is larger when Ξ”H∘\Delta H^\circ is large and when TT is low (through the 1/T21/T^2 factor in how small Ξ”T\Delta T steps accumulate).

Example. For an endothermic reaction, Ξ”H∘=+40.0Β kJ/mol\Delta H^\circ=+40.0\ \mathrm{kJ/mol} and K1=2.00K_1=2.00 at 300Β K300\ K. Estimate K at 330Β K330\ K, assuming constant reaction enthalpy, and distinguish this change from a catalyst’s effect.

Use ln⁑(K2/K1)=βˆ’(40000/8.314)(1/330βˆ’1/300)=1.46\ln(K_2/K_1)=-(40000/8.314)(1/330-1/300)=1.46. Thus K2=2.00e1.46β‰ˆ8.59K_2=2.00e^{1.46}\approx8.59. Heating favors the endothermic direction and changes equilibrium composition. A catalyst instead speeds the approach to equilibrium at a given temperature without changing its constant.


Le ChΓ’telier’s principle is a qualitative rule: if a stress disturbs an equilibrium, the system shifts in the direction that partially counteracts the stress (new equilibrium is established; KK is unchanged unless temperature changes).

Typical stresses:

  • Concentration: Adding a reactant shifts toward products; removing a product does the same. Adding product shifts toward reactants.
  • Pressure (gases): Reducing volume increases total pressure; the system shifts toward the side with fewer moles of gas (if any). Adding an inert gas at constant volume does not change partial pressures of reactants/productsβ€”no shift. At constant pressure, adding inert gas increases volume and can shift the equilibrium; AP questions usually emphasize the constant-volume case.
  • Temperature: KK changes with temperature. Treat heat as part of the reaction: for an endothermic forward reaction (Ξ”H>0\Delta H > 0), raising TT favors the forward direction (larger KK if the forward reaction is endothermic). For an exothermic forward reaction (Ξ”H<0\Delta H < 0), raising TT favors the reverse direction (smaller KK). Cooling favors the exothermic direction.

Since KK depends on TT, do not treat temperature like a simple concentration stress when you need a numerical KK: use the correct KK for the new temperature if given, compute K2K_2 from K1K_1 with the van’t Hoff equation (previous section), or reason qualitatively from Ξ”H\Delta H.

stressappliedsystemshiftstoreducestressconcentrationtemperaturepressure/volumeconsumeaddedspeciesorreplaceremovedspeciestreatheatlikereactantorproductfavorfewerormoregasmoles

Example. Inert gas is added to an ideal-gas equilibrium mixture at fixed temperature and fixed volume. Total pressure rises. Must equilibrium shift toward fewer gas molecules?

No. Each reacting species still has the same niRT/Vn_iRT/V partial pressure, so Q stays equal to K. Total pressure alone is insufficient. If instead volume increased at fixed total pressure, reacting-species partial pressures would change and a shift could occur.


ICE stands for Initial, Change, Equilibrium. You use a table to organize amounts (or concentrations) for one reversible process.

Setup:

  1. Write a balanced equation.
  2. Initial row: given starting concentrations (after any mixing).
  3. Change row: express unknown change as xx (or a multiple like 2x2x from stoichiometry): reactants lose (βˆ’jx-jx, etc.) and products gain (+lx+lx, etc.), although you could swap the signs and have the same result. Note that if one side is 0, it can’t lose any concentration, so it must have a positive change!
  4. Equilibrium row: Initial + Change.

Rules and tips:

  • Omit pure solids and pure liquids from the table if they do not define the solution volume.
  • If a reactant is limiting, one species may be consumed completely before equilibrium in a sequential sense; still check whether the reaction can proceed in reverse from that state (ICE applies to the equilibrium stage you model).
  • Small KK (product-poor): equilibrium lies left; xx may be negligible compared to initial concentrationsβ€”verify with the 5% rule (or exact quadratic) when your course allows.
  • Large KK: equilibrium lies right; sometimes you assume complete reaction first, then back-react a small amount.

When KK is small, very little reactant converts, so a term like 0.500βˆ’x0.500-x in the denominator is barely changed by xx. Approximating 0.500βˆ’xβ‰ˆ0.5000.500-x\approx0.500 turns an otherwise-quadratic (or worse) equation into one you can solve by simple algebra. The approximation is considered valid when

x[A]0Γ—100%≀5%,\frac{x}{[\text{A}]_0}\times100\% \le 5\%,

i.e. xx is at most 5%5\% of the initial concentration it was subtracted from. If the computed xx fails this test, the approximation is too roughβ€”go back and solve the quadratic exactly (or iterate). As a rough guide, the approximation is usually safe when [A]0/K≳400[\text{A}]_0/K \gtrsim 400.

StepReactantsProducts
Initialstarting concentrationsstarting concentrations
Changesubtract according to stoichiometryadd according to stoichiometry
Equilibriuminitial plus changeinitial plus change

For aA+bBβ‡ŒcC+dDaA+bB\rightleftharpoons cC+dD, changes usually look like βˆ’ax-ax, βˆ’bx-bx, +cx+cx, and +dx+dx.

Example. For Aβ‡ŒB+C\mathrm{A\rightleftharpoons B+C}, start with [A]=0.100Β M[A]=0.100\ M and no products, with Kc=0.0100K_c=0.0100. Test the small-change approximation and calculate the physical root if it fails.

Assuming 0.100βˆ’xβ‰ˆ0.1000.100-x\approx0.100 gives x=0.0100(0.100)=0.0316Β Mx=\sqrt{0.0100(0.100)}=0.0316\ M, or 31.6%31.6\% depletion, so the assumption fails. Instead solve x2/(0.100βˆ’x)=0.0100x^2/(0.100-x)=0.0100, giving x2+0.0100xβˆ’0.00100=0x^2+0.0100x-0.00100=0 and x=0.0270Β Mx=0.0270\ M. The negative root is unphysical because products start at zero. A small numerical K is not enough by itself; the change must be small relative to the starting concentration.


You might remember the solubility rules from Unit 4. For a sparingly soluble ionic solid (basically anything that is considered β€œinsoluble” to water), dissolution is an equilibrium. For example,

AmBl(s)β‡Œm Aa+(aq)+l Bbβˆ’(aq).\text{A}_m\text{B}_l(s) \rightleftharpoons m\,\text{A}^{a+}(aq) + l\,\text{B}^{b-}(aq).

The solubility product is

Ksp=[Aa+]m[Bbβˆ’]l.K_{sp} = [\text{A}^{a+}]^m [\text{B}^{b-}]^l.

The solid (precipitate) does not appear in KspK_{sp}. This is equivalent to KcK_c but for a dissolution.

Setting up an ICE table for KspK_{sp} is slightly different from a normal ICE table procedure.

Setup:

  1. Write a balanced equation for solubility (remember that the solid is ALWAYS on the left side).
  2. Initial row: given starting concentrations (after any mixing). For the concentration of the solid, just write β€œsolid” in that box.
  3. Change row: This is the same as a regular ICE table.
  4. Equilibrium row: This is the same as a regular ICE table, except write β€œsolid” for initial for the precipitate.

Example. For Ag2CrO4\mathrm{Ag_2CrO_4} dissolving in pure water, why is an ICE row of +s+s for both ions incorrect? Write the correct expression.

Each dissolved formula unit produces two silver ions and one chromate ion. Thus the concentration changes are +2s+2s for Ag+\mathrm{Ag^+} and +s+s for CrO42βˆ’\mathrm{CrO_4^{2-}}. With no initial ions, Ksp=(2s)2(s)=4s3K_{sp}=(2s)^2(s)=4s^3. The coefficient affects both the concentration produced and the exponent in the equilibrium expression; these are separate consequences of the same balanced equation.

Molar solubility (ss) is the number of moles of solid that dissolve per liter of solution to reach saturation (under stated conditions). If one formula unit of AmBl\text{A}_m\text{B}_l produces mm ions of A\text{A} and ll ions of B\text{B}, then at saturation

[Aa+]=ms,[Bbβˆ’]=ls,[\text{A}^{a+}] = ms, \qquad [\text{B}^{b-}] = ls,

and

Ksp=(ms)m(ls)l=mm ll sm+l.K_{sp} = (ms)^m (ls)^l = m^m\, l^l\, s^{m+l}.

Solve for ss given KspK_{sp}, or KspK_{sp} given ss. In an ICE table, the molar solubility is equivalent to the xx value.

Example. Two salts have the same numerical Ksp=1.0Γ—10βˆ’12K_{sp}=1.0\times10^{-12}. One dissociates as AB\mathrm{AB} and the other as AB2\mathrm{AB_2}. Are their molar solubilities equal in pure water?

No. For AB\mathrm{AB}, Ksp=s2K_{sp}=s^2 gives s=1.0Γ—10βˆ’6Β Ms=1.0\times10^{-6}\ M. For AB2\mathrm{AB_2}, Ksp=s(2s)2=4s3K_{sp}=s(2s)^2=4s^3 gives s=6.3Γ—10βˆ’5Β Ms=6.3\times10^{-5}\ M. Equal equilibrium constants do not imply equal formula-unit solubilities when dissociation stoichiometries differ. This assumes neither ion undergoes a significant additional reaction.

The ion product QspQ_{sp} uses current ion concentrations in the KspK_{sp} expression (same form as KspK_{sp}).

  • If Qsp<KspQ_{sp} < K_{sp}, the solution is unsaturated; more solid can dissolve.
  • If Qsp=KspQ_{sp} = K_{sp}, the solution is saturated (at equilibrium with solid, if present).
  • If Qsp>KspQ_{sp} > K_{sp}, precipitation occurs until QspQ_{sp} drops to KspK_{sp} (assuming equilibrium can be reached).

Example. Equal volumes of 2.0Γ—10βˆ’5Β M2.0\times10^{-5}\ M silver nitrate and 2.0Γ—10βˆ’5Β M2.0\times10^{-5}\ M sodium chloride are mixed. With Ksp(AgCl)=1.8Γ—10βˆ’10K_{sp}(\mathrm{AgCl})=1.8\times10^{-10}, does precipitation begin?

Mixing doubles each solution’s volume, so both ion concentrations become 1.0Γ—10βˆ’5Β M1.0\times10^{-5}\ M before any reaction. The ion product is Q=(1.0Γ—10βˆ’5)2=1.0Γ—10βˆ’10<KspQ=(1.0\times10^{-5})^2=1.0\times10^{-10}<K_{sp}, so precipitation is not predicted. Using the unmixed concentrations gives a false supersaturation result. Dilution must be accounted for before comparing QQ with KspK_{sp}.

If one of the ions is already present from another source (common ion), its higher initial concentration shifts dissolution left, lowering molar solubility compared to pure water. ICE-style reasoning applies: treat initial [Aa+][\text{A}^{a+}] or [Bbβˆ’][\text{B}^{b-}] as nonzero before the solid dissolves further.

Example. Solid AgCl is present in saturated solution. Add NaCl without appreciably changing the volume. Does the silver concentration decrease because KspK_{sp} decreases?

The temperature is unchanged, so KspK_{sp} remains constant. Added chloride initially makes Q=[Ag+][Clβˆ’]Q=[\mathrm{Ag^+}][\mathrm{Cl^-}] too large, causing precipitation until the product again equals KspK_{sp}. The new equilibrium has less dissolved silver and more chloride. Concentrations change to satisfy the same constant, rather than changing the constant to fit the disturbance.

Selective precipitation separates ions by adding a reagent that forms salts with very different KspK_{sp} values. The ion whose QspQ_{sp} exceeds its KspK_{sp} first (lowest KspK_{sp} or favorable stoichiometry) precipitates preferentially as concentration is raisedβ€”used analytically and conceptually on the exam.

Example. Two cations form 1:1 salts with anion X. Their initial concentrations are [M+]=0.100Β M[M^+]=0.100\ M and [N+]=0.00100Β M[N^+]=0.00100\ M, with Ksp(MX)=10βˆ’8K_{sp}(MX)=10^{-8} and Ksp(NX)=10βˆ’9K_{sp}(NX)=10^{-9}. Which salt begins precipitating first as X is added slowly?

The thresholds are [Xβˆ’]=10βˆ’8/0.100=10βˆ’7Β M[X^-]=10^{-8}/0.100=10^{-7}\ M for MX and 10βˆ’9/0.00100=10βˆ’6Β M10^{-9}/0.00100=10^{-6}\ M for NX. MX precipitates first despite its larger solubility-product constant. Precipitation onset depends on both the constant and the available cation concentration, not on ranking constants alone. These thresholds assume negligible dilution and no other significant reactions.


A complex ion consists of a central metal cation (Lewis acid) bound to ligands (Lewis bases) that donate electron pairs (learn more about acids/bases in Unit 8). In a solution, stepwise binding equilibria exist; textbooks often emphasize an overall formation (stability) constant KfK_f for

Mn++x Lβ‡ŒMLxn+,\text{M}^{n+} + x\,\text{L} \rightleftharpoons \text{ML}_x^{n+},

with

Kf=[MLxn+][Mn+][L]x,K_f = \frac{[\text{ML}_x^{n+}]}{[\text{M}^{n+}][\text{L}]^x},

matching the form of KcK_c for that net reaction (charges and stoichiometry depend on the specific complex). A larger KfK_f means the complex is more stable (more product-favored at equilibrium). If ligand is in large excess and KfK_f is large, it is often reasonable to assume complete formation for stoichiometry purposesβ€”check problem assumptions.

The dissociation constant KdK_d for breaking the complex apart is the reciprocal of KfK_f for the same net forward/back pairing:

Kf=1Kd.K_f = \frac{1}{K_d}.

Coordination number is the number of donor atoms bound to the metal; common geometries include linear (2), tetrahedral or square planar (4), and octahedral (6).


The same equilibrium-constant methods apply to acid–base (KaK_a, KbK_b, KwK_w) and buffers in the next unitβ€”only the chemical reaction and symbols change.

Example. Excess ligand binds dissolved metal ions from a sparingly soluble salt. Explain why total dissolved metal can rise while the free-metal concentration remains very small.

The ligand removes free metal ions by forming a complex. This lowers the ion product for dissolution, allowing more solid to dissolve. The solubility expression uses free metal ions, whereas total dissolved metal includes both free and complexed forms. Treating those concentrations as identical misses the effect.


  1. For A(g)β‡Œ2B(g)A(g)\rightleftharpoons2B(g) at equilibrium, volume is suddenly doubled at fixed temperature. What is Q immediately afterward?

    (A) K/2K/2
    (B) KK
    (C) 2K2K
    (D) 4K4K

  1. For Aβ‡ŒBA\rightleftharpoons B, K1=4K_1=4; for Bβ‡ŒCB\rightleftharpoons C, K2=9K_2=9. Find K for 2Cβ‡Œ2A2C\rightleftharpoons2A.

    (A) 1/361/36
    (B) 1/12961/1296
    (C) 3636
    (D) 12961296

  1. For MX2(s)β‡ŒM2++2Xβˆ’\mathrm{MX_2(s)\rightleftharpoons M^{2+}+2X^-} with Ksp=4.0Γ—10βˆ’12K_{sp}=4.0\times10^{-12}, what is molar solubility in pure water?

    (A) 2.0Γ—10βˆ’6Β M2.0\times10^{-6}\ M
    (B) 1.6Γ—10βˆ’4Β M1.6\times10^{-4}\ M
    (C) 1.0Γ—10βˆ’4Β M1.0\times10^{-4}\ M
    (D) 4.0Γ—10βˆ’12Β M4.0\times10^{-12}\ M

  1. Equal volumes of 2.0Γ—10βˆ’5Β M2.0\times10^{-5}\ M silver nitrate and sodium chloride are mixed. For AgCl, Ksp=1.8Γ—10βˆ’10K_{sp}=1.8\times10^{-10}. Does precipitation begin?

    (A) Yes, because Q is 4.0Γ—10βˆ’104.0\times10^{-10}
    (B) Yes, because Q is less than Ksp
    (C) No, because Ksp changes on mixing
    (D) No, because dilution makes Q 1.0Γ—10βˆ’101.0\times10^{-10}

  1. An equilibrium mixture contains solid calcium carbonate, solid calcium oxide, and carbon dioxide at fixed temperature and volume. More calcium carbonate is added without changing gas volume. What happens to equilibrium carbon dioxide pressure?

    (A) It doubles
    (B) It stays unchanged while both solid phases remain
    (C) It falls to zero
    (D) Kp increases

  1. A reaction has positive standard free energy but current Q<KQ<K. Which statement is correct?

    (A) Forward reaction is favorable under the current conditions
    (B) Reverse reaction must be favorable because standard free energy is positive
    (C) The system is at equilibrium
    (D) A catalyst must change K before forward reaction is possible

  1. At a certain temperature, Kc=4.00K_c=4.00 for
A(g)β‡Œ2B(g).\text{A}(g)\rightleftharpoons2\text{B}(g).

A sealed container initially has 0.600Β M0.600\ M A\text{A} and no B\text{B}.

(A)(A) Write the equilibrium-constant expression.

(B)(B) Set up an ICE table using xx for the amount of A\text{A} consumed.

(C)(C) Calculate the equilibrium concentrations of A\text{A} and B\text{B}.

(D)(D) Original extension. After equilibrium is reached, the container volume doubles at constant temperature. Calculate the immediate reaction quotient and determine the direction of the shift. Is the final concentration of B necessarily greater than before expansion? Explain.

  1. The 2024 AP Chemistry exam included an equilibrium particle-diagram question for H2(g)+I2(g)β‡Œ2HI(g)\text{H}_2(g)+\text{I}_2(g)\rightleftharpoons2\text{HI}(g). (Adapted from College Board, 2024 AP Chemistry FRQ 5.)

    (A)(A) Write the expression for QQ.

    (B)(B) If [H2]=0.20Β M[\text{H}_2]=0.20\ M, [I2]=0.10Β M[\text{I}_2]=0.10\ M, and [HI]=0.30Β M[\text{HI}]=0.30\ M, calculate QQ.

    (C)(C) If K=50K=50, predict the direction the system shifts.

    (D)(D) Original extension. Compress the mixture to half its volume at constant temperature. Calculate the new reaction quotient and decide whether compression changes the direction predicted in the earlier part.