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Statement I: For the reaction $N_2(g) + 3H_2(g) \rightleftharpoons 2NH_3(g)$, $K_p < K_c$.
Statement II: $K_p = K_c(RT)^{\Delta n_g}$ and for this reaction $\Delta n_g = -2$, so $K_p = K_c(RT)^{-2} < K_c$.
Options
1
Statement I is correct and II is incorrect
2
Both statements are correct and II is the correct explanation of I
3
Statement I is incorrect and II is correct
4
Both statements are incorrect
Correct Answer
Both statements are correct and II is the correct explanation of I
Solution
1

$\Delta n_g = 2 - (1+3) = 2 - 4 = -2$

$$K_p = K_c(RT)^{\Delta n_g} = K_c(RT)^{-2} = \frac{K_c}{(RT)^2}$$
2

At 300 K: $RT = 0.0821 \times 300 = 24.63$. So $(RT)^2 = 606$.

$K_p = K_c/606 \ll K_c$

Statement I is TRUE. Statement II gives the correct explanation. Answer: Both correct, II explains I

$\Delta n_g = -2$ → $K_p = K_c/(RT)^2$ → $K_p < K_c$
Theory: Equilibrium
1. Relationship between Kp and Kc

For a general gaseous reaction $aA(g) + bB(g) \rightleftharpoons cC(g) + dD(g)$: $K_p = K_c(RT)^{\Delta n_g}$ where $\Delta n_g = (c+d) - (a+b)$ = moles of gaseous products - moles of gaseous reactants. $R = 0.0821$ L·atm/(mol·K) or $R = 8.314$ J/(mol·K). Three cases: $\Delta n_g = 0$: $K_p = K_c$. Examples: H₂+I₂⇌2HI, N₂+O₂⇌2NO. $\Delta n_g > 0$: $K_p > K_c$ (e.g., PCl₅⇌PCl₃+Cl₂, $\Delta n_g=1$; N₂O₄⇌2NO₂, $\Delta n_g=1$; CaCO₃⇌CaO+CO₂, $\Delta n_g=1$). $\Delta n_g < 0$: $K_p < K_c$ (e.g., N₂+3H₂⇌2NH₃, $\Delta n_g=-2$; 2SO₂+O₂⇌2SO₃, $\Delta n_g=-1$). Derivation: using ideal gas law $P = nRT/V$, concentration $[A] = P_A/(RT)$. Substituting into $K_p$ expression and rearranging gives $K_p = K_c(RT)^{\Delta n_g}$.

2. Units of Equilibrium Constant

Strictly speaking, equilibrium constants are dimensionless. This is achieved by dividing each concentration by standard concentration $c^\circ = 1$ mol/L or each pressure by standard pressure $P^\circ = 1$ bar or 1 atm. $K_c = \prod_i ([A_i]/c^\circ)^{\nu_i}$ (numerically same as using concentrations in mol/L). $K_p = \prod_i (P_i/P^\circ)^{\nu_i}$ (dimensionless). In practice: use concentrations in mol/L for $K_c$ and pressures in atm or bar for $K_p$. The numerical value of $K_p$ depends slightly on the choice of pressure standard (1 atm vs 1 bar). The relationship $K_p = K_c(RT)^{\Delta n_g}$ uses $R = 0.0821$ L·atm/(mol·K) when pressure is in atm and concentration in mol/L.

3. Le Chatelier and Industrial Applications

Understanding $K_p$ vs $K_c$ has practical implications: Haber process ($N_2+3H_2 \to 2NH_3$, $\Delta n_g = -2$): $K_p << K_c$. At high pressures, $K_p$ is calculated but partial pressures are relevant for yield calculation. Increasing total pressure at constant temperature: doesn't change $K_p$ (constant at constant T), but shifts reaction forward (Le Chatelier: fewer moles of gas). Contact process ($2SO_2+O_2 \to 2SO_3$, $\Delta n_g=-1$): $K_p = K_c/(RT)$. High pressure also favours SO₃ production. Dissociation of N₂O₄ ($N_2O_4 \to 2NO_2$, $\Delta n_g=+1$): $K_p > K_c$. Decreasing pressure shifts forward (more moles of gas).

4. Degree of Dissociation from Kp

For $A(g) \rightleftharpoons nB(g)$ starting with 1 mole A at pressure P: At equilibrium: A = $1-\alpha$, B = $n\alpha$, total = $1+(n-1)\alpha$. Mole fractions: $x_A = (1-\alpha)/(1+(n-1)\alpha)$, $x_B = n\alpha/(1+(n-1)\alpha)$. Partial pressures: $P_A = x_A P$, $P_B = x_B P$. $K_p = P_B^n/P_A = (n\alpha P/(1+(n-1)\alpha))^n / ((1-\alpha)P/(1+(n-1)\alpha))$. For PCl₅ ⇌ PCl₃ + Cl₂ ($n=2$ products): $K_p = \alpha^2 P/(1-\alpha^2)$. At higher P: $K_p$ unchanged (constant T) but $\alpha$ decreases (Le Chatelier: more pressure → less dissociation). At lower P: $\alpha$ increases. For N₂O₄ ⇌ 2NO₂: $K_p = 4\alpha^2 P/(1-\alpha^2)$. Brown colour of NO₂ intensifies at low pressure (more dissociation).

5. Thermodynamics and Equilibrium

$\Delta G^\circ = -RT\ln K = -2.303RT\log K$. At 298 K: $\Delta G^\circ = -5.7\log K$ kJ/mol. If $K > 1$: $\log K > 0$, $\Delta G^\circ < 0$ (products favoured). If $K < 1$: $\Delta G^\circ > 0$ (reactants favoured). If $K = 1$: $\Delta G^\circ = 0$ (equal products and reactants). $\Delta G = \Delta G^\circ + RT\ln Q$. At equilibrium: $\Delta G = 0$, $Q = K$. Van't Hoff equation: $\frac{d\ln K}{dT} = \frac{\Delta H^\circ}{RT^2}$. Integrating: $\ln\frac{K_2}{K_1} = \frac{\Delta H^\circ}{R}\left(\frac{1}{T_1} - \frac{1}{T_2}\right)$. If $\Delta H^\circ > 0$: $K$ increases with $T$. If $\Delta H^\circ < 0$: $K$ decreases with $T$. This is Le Chatelier's principle in quantitative form.

6. Heterogeneous Equilibria

Heterogeneous equilibria involve species in more than one phase. Pure solids and pure liquids are NOT included in the equilibrium constant expression (their activities = 1, concentration is constant within the pure phase). $CaCO_3(s) \rightleftharpoons CaO(s) + CO_2(g)$: $K_p = P_{CO_2}$, $K_c = [CO_2]$. The equilibrium depends only on $P_{CO_2}$, not on amounts of CaCO₃ or CaO present. $C(s) + H_2O(g) \rightleftharpoons CO(g) + H_2(g)$: $K_p = P_{CO} \cdot P_{H_2}/P_{H_2O}$. $FeO(s) + CO(g) \rightleftharpoons Fe(s) + CO_2(g)$: $K_p = P_{CO_2}/P_{CO}$. For dissolution: $AgCl(s) \rightleftharpoons Ag^+(aq) + Cl^-(aq)$: $K = K_{sp} = [Ag^+][Cl^-]$ (water activity = 1).

7. Multiple Equilibria

When reactions are combined, equilibrium constants multiply. If: Reaction 1: A ⇌ B, $K_1$. Reaction 2: B ⇌ C, $K_2$. Then overall: A ⇌ C, $K = K_1 K_2$. If Reaction 1 reversed: B ⇌ A, $K = 1/K_1$. If Reaction 1 multiplied by $n$: $nA ⇌ nB$, $K = K_1^n$. Applications: Hess law for $K$ values. Stepwise formation constants of complexes: $\beta_n = \beta_1 \times \beta_2 \times ... \times \beta_n$. For acid-base equilibria: $K_a \times K_b = K_w$ (for conjugate acid-base pair). This is why stronger acid has weaker conjugate base.

8. Common Ion Effect on Equilibria

Adding an ion that is already involved in the equilibrium shifts the equilibrium according to Le Chatelier. Common ion effect reduces solubility: AgCl(s) ⇌ Ag⁺+Cl⁻. Adding NaCl → [Cl⁻] increases → Q > K → equilibrium shifts back → less AgCl dissolves. Common ion effect in buffer solutions: CH₃COOH ⇌ CH₃COO⁻ + H⁺. Adding CH₃COONa (common CH₃COO⁻) → [CH₃COO⁻] increases → Q > K → shift back (fewer H⁺ → higher pH). This is how buffer works. Common ion effect in precipitation: adding excess precipitating ion to remove a specific cation completely from solution. In qualitative analysis: adding excess Cl⁻ in Group I ensures complete precipitation of Ag⁺, Pb²⁺, Hg₂²⁺.

Frequently Asked Questions
1. How is the Kp = Kc(RT)^Δng formula derived?
For the reaction $aA(g) + bB(g) \rightleftharpoons cC(g) + dD(g)$: $K_p = \dfrac{(P_C)^c(P_D)^d}{(P_A)^a(P_B)^b}$. Using ideal gas law: $P_i = [i]RT$ for each gas $i$. Substituting: $K_p = \dfrac{([C]RT)^c([D]RT)^d}{([A]RT)^a([B]RT)^b} = \dfrac{[C]^c[D]^d}{[A]^a[B]^b} \times (RT)^{(c+d)-(a+b)} = K_c \cdot (RT)^{\Delta n_g}$. This derivation assumes ideal gas behaviour ($PV = nRT$). At high pressures or low temperatures, real gas deviations can cause slight discrepancies.
2. Calculate Kp from Kc for specific example
For N₂+3H₂⇌2NH₃ at 500°C (773 K): if $K_c = 6.0\times10^{-2}$ mol⁻² L². $\Delta n_g = 2-4 = -2$. $K_p = K_c(RT)^{-2} = \dfrac{K_c}{(RT)^2}$. $RT = 0.0821\times773 = 63.5$ L·atm/mol. $(RT)^2 = 4032$. $K_p = 6.0\times10^{-2}/4032 = 1.49\times10^{-5}$ atm⁻². $K_p << K_c$ by factor ~4000. At higher temperatures, $RT$ is larger, so the ratio $K_p/K_c = (RT)^{-2}$ is even smaller. This shows how important the temperature-dependent $(RT)^{\Delta n_g}$ factor is.
3. What happens to Kp if temperature changes?
$K_p$ changes with temperature according to van't Hoff equation: $d\ln K_p/dT = \Delta H^\circ/(RT^2)$. For Haber process ($\Delta H = -92$ kJ/mol, exothermic): increasing T decreases $K_p$ (less NH₃ at higher T). At 25°C: $K_p \approx 6\times10^5$ atm⁻². At 500°C: $K_p \approx 6\times10^{-5}$ atm⁻². Decrease of $10^{10}$! This is why the Haber process operates at 400-500°C as a compromise — below 300°C: $K$ is large but rate too slow; above 600°C: $K$ is too small for acceptable yield. Note: $K_c$ also changes with T in the same direction, since $K_p = K_c(RT)^{-2}$, and both change together.
4. When does Kp = Kc exactly?
$K_p = K_c$ when $\Delta n_g = 0$, i.e., $(RT)^0 = 1$. This occurs when the total number of moles of gaseous products equals total moles of gaseous reactants. Examples: H₂(g) + I₂(g) ⇌ 2HI(g): $\Delta n_g = 2-2 = 0$. N₂(g) + O₂(g) ⇌ 2NO(g): $\Delta n_g = 2-2 = 0$. CO(g) + H₂O(g) ⇌ CO₂(g) + H₂(g) (water-gas shift): $\Delta n_g = 2-2 = 0$. For all these: $K_p = K_c$ at any temperature. Also note: solids and liquids don't count in $\Delta n_g$ calculation — only gaseous species.
5. How is Kp related to equilibrium yield for Haber process?
At 500°C and 300 atm with $K_p = 6\times10^{-5}$: using $K_p = \alpha^2 P^{-2} \times$ correction factors... For stoichiometric N₂:H₂=1:3 feed: if $\alpha$ = fraction of N₂ converted, then at equilibrium $n_{total} = (1-\alpha)+3(1-\alpha)+2\alpha = 4-2\alpha$ moles from 4 initial moles. Mole fractions: $x_{N_2} = (1-\alpha)/(4-2\alpha)$, $x_{H_2} = 3(1-\alpha)/(4-2\alpha)$, $x_{NH_3} = 2\alpha/(4-2\alpha)$. At 300 atm: solving $K_p = 6\times10^{-5}$ gives $\alpha \approx 0.35$ (35% conversion). In practice, unreacted N₂ and H₂ are recycled → overall yield much higher despite low single-pass conversion.
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