Great — I’ll convert those 60 items into detailed, long-answer style solutions suitable for university
exams (full derivations, explanations, worked examples where relevant). I’ll keep each answer complete and
exam-ready, with clear steps and final boxed results where calculations are involved.
Because this is long, I’m grouping answers by Unit and numbering consistently. If you want any single
answer expanded further (extra examples, diagrams, or a printable PDF), tell me which question numbers
and I’ll expand those next.
SEM-I PHYSICAL CHEMISTRY — 60 Long-
Answer Solutions
Unit I — Chemical Equilibrium (Questions 1–20)
1. Law of Mass Action; equilibrium constant for (\ce{aA +
bB <=> cC + dD})
Answer (long):
The Law of Mass Action (Guldberg & Waage) states: At a given temperature, the rate of a chemical
reaction is proportional to the product of the active masses (for gases: partial pressures; for solutes:
concentrations) of the reactants each raised to a power equal to its stoichiometric coefficient in the
balanced equation. For the general reversible reaction
[
\ce{aA + bB <=> cC + dD},
]
let the equilibrium concentrations be ([A]{eq}, [B]{eq}, [C]{eq}, [D]{eq}). The equilibrium constant in terms of
concentration is defined as
[
\boxed{K_c=\frac{[C]{eq}^c,[D]{eq}^d}{[A]{eq}^a,[B]{eq}^b}}
]
provided activities concentrations (ideal dilute solutions). For gaseous systems, the equilibrium constant in
terms of partial pressures is
[
\boxed{K_p=\frac{(P_C)^c (P_D)^d}{(P_A)^a (P_B)^b}}.
]
Interpretation: (K) depends only on temperature, not on initial amounts. If (K\gg1) products are favored;
if (K\ll1) reactants are favored. The derivation follows from equating forward and reverse rates for
elementary steps (kinetic viewpoint) or from thermodynamic condition (\Delta G = 0) at equilibrium using
(\mu_i = \mu_i^\circ + RT\ln a_i).
2. Derive relation between (K_p) and (K_c)
Answer (long):
For ideal gases, concentration (molarity) and partial pressure are related via ( [X] = \dfrac{P_X}{RT}) (in mol
L(^{-1}) if P in atm, R = 0.082057 L·atm·K ¹·mol ¹). For reaction (\ce{aA + bB <=> cC + dD}),
[
K_c = \frac{[C]^c [D]^d}{[A]^a [B]^b} = \frac{(P_C/RT)^c (P_D/RT)^d}{(P_A/RT)^a (P_B/RT)^b}.
]
Collecting ((RT)) factors:
[
K_c = \frac{P_C^c P_D^d}{P_A^a P_B^b} (RT)^{-(c+d-a-b)} = K_p (RT)^{-\Delta n},
]
where (\Delta n =) (moles gaseous products − moles gaseous reactants). Rearranged:
[
\boxed{K_p = K_c (RT)^{\Delta n}.}
]
Use: If (\Delta n = 0), then (K_p = K_c). This relation is valid for ideal gases and when K expressed with
partial pressures vs concentrations.
3. (\ce{PCl5(g) <=> PCl3(g) + Cl2(g)}) — find (K_p) given
initial and equilibrium pressures
Problem statement: Initial (P_{PCl5}=1.00) atm. At equilibrium (P_{PCl5}=0.60) atm. Find (K_p).
Solution (detailed): Let the dissociation be (x =) amount (in atm) of PCl(_5) that dissociates. Initially
PCl(_5) = 1.00; at eqn PCl(_5) = 0.60 (x=1.00-0.60=0.40) atm. Stoichiometry: for each mole PCl(_5)
dissociated, 1 mole PCl(_3) and 1 mole Cl(_2) are formed. So at equilibrium:
[
P_{PCl3}=x=0.40\ \text{atm},\quad P_{Cl2}=x=0.40\ \text{atm},\quad P_{PCl5}=0.60\ \text{atm}.
]
Compute:
[
K_p=\frac{P_{PCl3}\cdot P_{Cl2}}{P_{PCl5}}=\frac{0.40\times0.40}{0.60}=\frac{0.16}{0.60}
=0.266666\ldots
]
Round sensibly: (\boxed{K_p\approx 0.267}). (Units: dimensionless if pressures expressed relative to
standard pressure; otherwise report numerical K_p.)
Remarks: If total pressure changes or nonideal gas behavior significant, corrections needed.
4. Le Châtelier’s principle — explanation and
concentration example
Answer (long):
Statement: When a system at equilibrium experiences a change in concentration, pressure, volume, or
temperature, the system shifts in the direction that tends to oppose the imposed change, re-establishing
equilibrium.
Qualitative rationale: Equilibrium is a point where forward and reverse rates match. A perturbation
unbalances rates; the system shifts to re-balance.
Concentration example — derivation-style: Consider (\ce{A <=> B}) with equilibrium concentrations
([A]_e,\ [B]e). Add additional A (instantaneous [A] > ([A]e)). Now the forward rate (r_f = k_f[A]) increases
while reverse rate (r_b = k_b[B]) remains same momentarily net forward reaction occurs converting A B
until a new equilibrium with larger [B], smaller [A] (relative) is achieved such that (k_f[A]{new}=k_b[B]
{new}). The equilibrium constant (K) (as ratio of concentrations) remains the same if temperature
unchanged.
Worked micro-example: For gas-phase (\ce{N2O4 <=> 2 NO2}), adding NO(_2) increases Q, so system
shifts left forming N(_2)O(_4).
5. Effect of increasing total pressure on (\ce{N2 + 3H2 <=>
2NH3})
Answer (long):
Equation: (\ce{N2 + 3H2 <=> 2NH3}). Gas moles: reactants = 4, products = 2 (\Delta n = -2). According
to Le Châtelier, increasing pressure (by compressing volume) favors the side with fewer gas moles — here
products (NH(_3)). Hence equilibrium shifts right, increasing ammonia yield.
Thermodynamic note: For ideal gases, K_p depends only on T. Increasing pressure doesn't change K_p
but changes partial pressures and reaction quotient Q; shift happens to restore Q = K_p.
Industrial application (Haber): High pressure used to favor NH(_3) formation; compromise between
equilibrium yield and engineering cost.
6. Effect of adding inert gas at constant volume on
equilibrium
Answer (long):
Adding an inert gas at constant volume increases total pressure but does not change the partial pressures
of reactive gases (since mole fractions remain same, and P_total increases but partial pressures (P_i = y_i
P_{total}) remain proportional; however at constant volume, if inert gas added, mole fractions of reactive
species decrease — careful!). Two common statements exist; clarify:
If inert gas is added at constant volume but without changing moles of reactants/products, total
pressure increases and partial pressures of reactants/products remain same only if mole fractions
unchanged — this occurs only if inert gas is added while keeping the amounts of reactive gases
constant and temperature unchanged; partial pressures stay the same because each reactive gas partial
pressure depends solely on its mole and volume. Practically: adding inert gas into a fixed-volume vessel
increases total pressure but the partial pressures of the reactive gases (determined by their mole
numbers and fixed volume) remain unchanged so no shift in equilibrium.
If inert gas added at constant pressure (i.e., volume allowed to expand), partial pressures of reactants
get diluted equilibrium can shift if n 0.
Conclusion (standard exam answer): At constant volume, adding an inert gas does not affect equilibrium
position. At constant pressure it can shift equilibrium.
7. Degree of dissociation (\alpha) — derivation for (\ce{HA
<=> H+ + A-})
Answer (long):
Let initial concentration of HA be (c) mol·L ¹. At equilibrium degree of dissociation is (\alpha) (fraction
dissociated). Then
[
[HA]{eq}=c(1-\alpha),\quad [H^+]{eq}=[A^-]_{eq}=c\alpha.
]
The acid dissociation constant:
[
K_a = \frac{[H^+][A^-]}{[HA]}=\frac{(c\alpha)(c\alpha)}{c(1-\alpha)}=\frac{c\alpha^2}{1-\alpha}.
]
So exact relation:
[
\boxed{K_a=\frac{c\alpha^2}{1-\alpha}}.
]
For weak acids where (\alpha\ll 1), (1-\alpha \approx 1), yielding Ostwald’s dilution approximation:
[
\alpha \approx \sqrt{\frac{K_a}{c}}.
]
Example: acetic acid (K_a=1.8\times10^{-5}), (c=0.10) M (\alpha \approx \sqrt{1.8\times10^{-4}} \approx
0.0134) (1.34%).
8. Abnormal molecular mass — association/dissociation
causes
Answer (long):
Definition: The experimentally determined molecular mass (e.g., from vapor density, colligative properties)
that deviates from the expected molecular mass under ideal conditions is called abnormal molecular
mass. Causes:
Association in vapor: Monomers associate to form dimers/oligomers (e.g., acetic acid vapor
dimerization). Observed molar mass > expected.
Dissociation: A compound dissociates into smaller gaseous species (e.g., ammonium chloride partially
dissociates into NH(_3) + HCl) giving observed molar mass < expected.
Vapor density method: Apparent molecular mass (M_{app} = \dfrac{mass}{moles}) from PV = nRT. If
degree of association/dissociation present, algebraic relations yield M_app in terms of and true
molecular mass. Knowledge of allows correction to get true molar mass and equilibrium constant for
association/dissociation.
Worked conceptual example: For dimerization (2A A_2) with degree of association (fraction of
monomer associated), derive relations between observed vapor density and (left as exercise).
9. Reaction quotient (Q) and predicting direction
Answer (long):
Definition: Reaction quotient (Q) is defined using the same algebraic expression as (K) but using
instantaneous (not necessarily equilibrium) concentrations or partial pressures.
For (\ce{aA + bB <=> cC + dD}),
[
Q=\frac{[C]^c[D]^d}{[A]^a[B]^b}\quad(\text{or use partial pressures }Q_p).
]
Prediction rule:
If (Q < K): Reaction proceeds forward (toward products) to reach equilibrium.
If (Q > K): Reaction proceeds backward (toward reactants).
If (Q = K): System at equilibrium.
Example numeric: For (\ce{CO + H2O <=> CO2 + H2}), suppose instantaneous partial pressures lead to
(Q = 2.5\times10^{-3}) while K = 0.1 Q < K reaction will produce CO(_2) and H(_2) (shift right).
10. (\Delta G^\circ) — (K) relationship and interpretation
of sign
Answer (long):
From thermodynamics, at standard state:
[
\Delta G^\circ = -RT\ln K.
]
Where (R) = 8.314 J·mol ¹·K ¹ and T in K. Equivalently,
[
K = e^{-\Delta G^\circ/RT}.
]
Interpretation:
If (\Delta G^\circ < 0): (K > 1) — products favored at equilibrium under standard conditions.
If (\Delta G^\circ > 0): (K < 1) — reactants favored.
If (\Delta G^\circ = 0): (K = 1) — neither favored.
Worked example: (\Delta G^\circ = -11.4) kJ·mol ¹ at 298 K (K = e^{11400/(8.314×298)}) etc
(compute accordingly).
11. (\ce{N2O4 <=> 2NO2}), given (K_c), find [NO(_2)] at
equilibrium (worked quadratic)
Problem statement: (K_c = 4.0\times10^{-2}). Initial [N(_2)O(_4)]=0.10 M. Find [NO(_2)] at equilibrium.
Solution (stepwise): Let degree dissociation be . Then equilibrium:
[
[N_2O_4]=0.10(1-\alpha),\qquad [NO_2]=2\times0.10\alpha =0.20\alpha.
]
Plug into (K_c):
[
K_c=\frac{[NO_2]^2}{[N_2O_4]}=\frac{(0.20\alpha)^2}{0.10(1-\alpha)}=\frac{0.04\alpha^2}{0.10(1-\alpha)}
=\frac{0.4\alpha^2}{1-\alpha}.
]
Set equal:
[
\frac{0.4\alpha^2}{1-\alpha}=4.0\times10^{-2}.
]
Multiply both sides by (1-\alpha):
[
0.4\alpha^2 = 0.04(1-\alpha) =0.04 -0.04\alpha.
]
Rearrange:
[
0.4\alpha^2 +0.04\alpha -0.04 = 0.
]
Divide by 0.04:
[
10\alpha^2 + \alpha -1 = 0.
]
Solve quadratic: (\alpha = \dfrac{-1 \pm \sqrt{1 + 40}}{20} = \dfrac{-1 \pm \sqrt{41}}{20}). Positive root:
[
\alpha = \frac{-1 + 6.403124}{20} = \frac{5.403124}{20} = 0.270156.
]
Thus ([NO_2] = 0.20\alpha = 0.05403\ \text{M}.\quad\boxed{[NO_2] = 5.403\times10^{-2}\ \text{M}}.
Remarks: Keep algebra steps neat in exams; show discriminant and root selection.
12. Why pure solids/liquids omitted from equilibrium
expressions
Answer (long):
Thermodynamically, the activity (a_i) of a pure solid or pure liquid in its standard state is unity ((a = 1))
and does not change with the amount of that pure phase present (provided some remains). Since
equilibrium expressions are written in terms of activities, the activity of pure solids/liquids contributes a
multiplicative constant of 1 and is therefore omitted. Example: For (\ce{CaCO3(s) <=> CaO(s) + CO2(g)}),
[
K_p = a_{CO2} = p_{CO2} / p^\circ,
]
and the activities of CaCO(_3) and CaO dropped out.
Important caveat: If solids are non-pure or significantly non-ideal (impure, nonstoichiometric), effective
activities may not equal 1 — but for standard equilibrium problems pure solids/liquids are omitted.
13. Common-ion effect — explanation and quantitative
example (acetic acid + acetate)
Answer (long):
Concept: Addition of an ion common to an equilibrium suppresses the extent of that equilibrium (Le
Châtelier). For a weak acid ( \ce{HA <=> H+ + A^-}), adding (A^-) (e.g., sodium acetate) shifts equilibrium
left, reducing [H(^+)] and hence increasing pH.
Quantitative demonstration: Let initial acetic acid concentration 0.10 M, (K_a = 1.8\times10^{-5}).
Without salt: Assuming small , ([H^+] \approx \sqrt{K_a c} = \sqrt{1.8\times10^{-6}} =
1.3416\times10^{-3}) pH 2.87.
With 0.10 M sodium acetate added: ([A^-] \approx 0.10) initially; if acid dissociation small,
([HA]\approx0.10). Use equilibrium expression:
[
[H^+] = \frac{K_a [HA]}{[A^-]} \approx \frac{1.8\times10^{-5}\times0.10}{0.10}=1.8\times10^{-5}.
]
pH = −log(1.8×10 ⁵) 4.74. Conclusion: pH shifted from 2.87 to 4.74 — strong buffering action.
Exam note: Show algebra and state approximations explicitly.
14. Buffer solutions and Henderson–Hasselbalch equation
Answer (long):
Buffer definition: A buffer is a solution that resists changes in pH when small amounts of acid or base are
added; typically composed of a weak acid and its conjugate base or a weak base and its conjugate acid.
Derivation of Henderson–Hasselbalch: For acid dissociation ( \ce{HA <=> H+ + A^-}) with (K_a =
\dfrac{[H^+][A^-]}{[HA]}). Rearranged:
[
[H^+] = K_a \frac{[HA]}{[A^-]}.
]
Take negative log:
[
\mathrm{pH} = \mathrm{p}K_a + \log\frac{[A^-]}{[HA]}.
]
This is the Henderson–Hasselbalch equation. For buffer design, choose concentrations such that ([A^-]/
[HA]) yields desired pH. Working range typically pK_a ± 1.
Example: To prepare pH 4.76 using acetic acid (pK_a 4.76), require ([A^-] = [HA]) (ratio =1). Practical
preparations use e.g. 0.1 M CH(_3)COOH + 0.1 M CH(_3)COONa.
Limitations: Uses concentrations instead of activities; valid for moderately dilute solutions.
15. Temperature effect on equilibrium; van ’t Hoff
differential form
Answer (long):
Thermodynamic relation:
[
\Delta G^\circ = \Delta H^\circ - T\Delta S^\circ = -RT\ln K.
]
Thus,
[
\ln K = -\frac{\Delta H^\circ}{RT} + \frac{\Delta S^\circ}{R}.
]
Differentiate with respect to T:
[
\frac{d\ln K}{dT} = \frac{\Delta H^\circ}{RT^2}
]
(assuming H° and S° approximately constant over small T range). This is the van ’t Hoff equation
(differential form). Implications:
If (\Delta H^\circ > 0) (endothermic), (d\ln K/dT > 0) K increases with T.
If (\Delta H^\circ < 0) (exothermic), K decreases with T.
Integrated form (between T and T ):
[
\ln\frac{K_2}{K_1} = -\frac{\Delta H^\circ}{R}\left(\frac{1}{T_2}-\frac{1}{T_1}\right).
]
Exam practice: Use van ’t Hoff plots (ln K vs 1/T) to find H° (slope = − H°/R) and S° (intercept = S°/R).
16. Ionic product of water (K_w) and temperature
dependence
Answer (long):
Autoionization: (\ce{H2O <=> H+ + OH-}). Ionic product:
[
K_w = [H^+][OH^-].
]
At 25°C, (K_w = 1.0\times10^{-14}). Since autoionization is endothermic, increasing temperature increases
(K_w) (more ionization). Consequently neutral pH (pH where [H ] = [OH ]) changes: pH_neutral = ½
pK_w; at higher T pK_w decreases pH_neutral < 7.0. Always remember: neutral necessarily pH 7 at T
25°C.
17. For (\ce{2SO3 <=> 2SO2 + O2}) — n and pressure
effect
Answer (long):
Reaction: (\ce{2SO3 <=> 2SO2 + O2}). Gas moles: products = 3 (2 SO + 1 O ), reactants = 2 (\Delta n =
1). Increasing pressure favors side with fewer moles (reactants), so equilibrium shifts left (more SO ).
Conversely decreasing pressure favors products.
Thermodynamic note: K_p only depends on T. Pressure change modifies partial pressures and Q, causing
a shift until Q = K_p again.
18. Metastable (supersaturated) solution — preparation and
triggering crystallization
Answer (long):
Metastable/supersaturated definition: A solution whose solute concentration exceeds equilibrium
solubility at a given T but remains in solution due to kinetic barriers (no nucleation). It is not the
thermodynamically most stable state but persists.
Preparation: Dissolve solute at an elevated temperature to create a saturated hot solution; cool slowly
without disturbing or seeding to a temperature where solubility is lower — a metastable supersaturated
solution forms if nucleation avoided.
Triggering crystallization: Add a seed crystal, introduce foreign particle (heterogeneous nucleation),
scratch container walls, or vigorous stirring. Once nucleation begins, rapid precipitation (exothermic often)
occurs until equilibrium solubility restored.
Examples: Sodium acetate trihydrate supercooled solutions; sugar solutions in candy making.
19. Compute K from (\Delta G^\circ = +11.4) kJ·mol ¹ at
298 K
Answer (detailed calculation):
Given (\Delta G^\circ = +11.4\ \text{kJ·mol}^{-1} = 11400\ \text{J·mol}^{-1}). Use
[
K = e^{-\Delta G^\circ/(RT)}.
]
Compute denominator (RT = 8.314462618\ \text{J·mol}^{-1}\text{K}^{-1} \times 298\ \text{K}).
Do arithmetic step-by-step:
(8.314462618 \times 298 = 8.314462618 \times 300 - 8.314462618 \times 2).
(8.314462618 \times 300 = 2494.3387854).
(8.314462618 \times 2 = 16.628925236).
Subtract: (2494.3387854 - 16.628925236 = 2477.709860164) (2477.71\ \text{J·mol}^{-1}).
Exponent:
[
-\frac{11400}{2477.71} = -4.6026\ (\text{approx}).
]
So (K = e^{-4.6026}). Compute e^-4.6026:
e^-4 = 0.018315
refine using a calculator mentally: e^-4.6026 0.0100.
Thus (\boxed{K \approx 1.00\times10^{-2}}).
Interpretation: K 1; reactants favored at standard conditions.
20. Experimental methods to determine equilibrium
constant (three with details)
Answer (long):
Here are three widely used experimental approaches, with principles and practicality:
1.
Spectrophotometry
Principle: One species (reactant or product) absorbs light at a characteristic wavelength. Using
Beer–Lambert law (A = \varepsilon \ell c) we determine concentration from absorbance.
Procedure: Equilibrate mixture at constant T; measure absorbance at _max; calibrate using
standards; compute equilibrium concentrations calculate K.
Limitations: Requires distinct absorbing species, linear range of Beer–Lambert, negligible spectral
interference, and known molar absorptivity.
2.
Manometry/Gas analysis
Principle: For gas-phase equilibria, measure partial pressures of gaseous components directly
(manometer) or via gas chromatography.
Procedure: Start with known amounts; allow to equilibrate at constant T; measure partial pressures
of reactants/products; compute K_p.
Limitations: Requires leak-tight system, ideal gas assumptions, corrections for nonideal behavior at
high pressure.
3.
Conductivity (electrolytic equilibria)
Principle: Ionic concentrations determine electrical conductivity. For equilibria involving ionization
(weak acid/base), equilibrium concentrations deduced from conductivity measurements.
Procedure: Measure conductance of solution; determine molar conductance and degree of
dissociation (using limiting molar conductivities) compute K_a, K_b, K_sp etc.
Limitations: Accurate cell constant, temperature control, ionic strength effects, and electrode
polarization to be managed.
Exam tip: For each method briefly state calibration, sources of systematic error, and how temperature
control is crucial.
Unit II — Chemical Kinetics (Questions 21–40)
21. Define reaction rate; general rate law for (aA + bB \to)
products
Answer (long):
Reaction rate is the change in concentration of a reactant or product per unit time. For reactant A:
[
\text{Rate} = -\frac{1}{a}\frac{d[A]}{dt},
]
where (a) is stoichiometric coefficient for A. The general form of empirical rate law (for many reactions):
[
\text{Rate} = k [A]^m [B]^n \ldots
]
Where (k) is the rate constant (depends on T), and exponents (m,n) are reaction orders (determined
experimentally, not necessarily equal to stoichiometric coefficients except for elementary reactions).
Overall order = (m+n+\cdots).
Remarks: Rate laws can be determined by the method of initial rates, isolation method, or integrated rate
laws.
22. Order vs molecularity — differences with examples
Answer (long):
Order of reaction
Defined from rate law exponents.
Can be zero, integer or fractional.
Determined experimentally.
Example: Rate = (k[A]^1 [B]^0) first order in A, zero order in B; overall order 1.
Molecularity
Number of molecules participating in an elementary step (uni-, bi-, tri-molecular).
Integer and applies to elementary steps only.
Example: Elementary bimolecular reaction (\ce{A + B -> products}) has molecularity 2.
Key differences: Order is empirical and global for the overall rate; molecularity is theoretical and local for
an elementary process. Overall order may not equal stoichiometric coefficients unless reaction is
elementary.
23. Integrated rate law for first-order reaction and half-life
derivation
Answer (long):
For first-order decomposition (A \rightarrow) products, rate law:
[
-\frac{d[A]}{dt} = k[A].
]
Separate and integrate from (t=0) to (t=t):
[
\int_{[A]_0}^{[A]_t}\frac{d[A]}{[A]} = -k\int_0^t dt \quad\Rightarrow\quad \ln\frac{[A]_t}{[A]_0} = -kt.
]
Thus
[
\boxed{[A]_t = [A]_0 e^{-kt}}.
]
Half-life (t_{1/2}): when ([A]_t = \tfrac{1}{2}[A]_0),
[
\frac{1}{2} = e^{-k t_{1/2}} \Rightarrow t_{1/2} = \frac{\ln 2}{k}.
]
Properties: First-order half-life independent of initial concentration.
24. Given (t_{1/2} = 138) s, find k
Answer (calculation with digits): Use (k = \dfrac{\ln 2}{t_{1/2}}).
Compute stepwise:
(\ln 2 = 0.69314718).
(k = 0.69314718 / 138 = 0.0050210\ \text{s}^{-1}).
Round appropriately: (\boxed{k \approx 5.02\times10^{-3}\ \text{s}^{-1}}).
Exam tip: show both formula and arithmetic steps.
25. Zero-order reactions: integrated form and half-life
dependence
Answer (long):
Zero-order rate law: (-\dfrac{d[A]}{dt} = k) (k constant).
Integrate:
[
[A]_t = [A]_0 - kt.
]
Half-life: (t_{1/2} = \dfrac{[A]_0}{2k}) — depends linearly on initial concentration; unique feature compared
to first-order.
Examples: Catalytic decomposition with saturated surface; photochemical reactions under constant photon
flux approximations.
26. Integrated form for second-order reaction (2A
\rightarrow) products
Answer (long):
Rate law: (-\dfrac{d[A]}{dt} = k[A]^2). Separate and integrate:
[
\int_{[A]_0}^{[A]_t} \frac{d[A]}{[A]^2} = -k\int_0^t dt \quad\Rightarrow\quad -\left(\frac{1}{[A]_t} - \frac{1}
{[A]_0}\right) = -kt,
]
so
[
\boxed{\frac{1}{[A]_t} = \frac{1}{[A]_0} + kt}.
]
(For (2A\to) products sometimes the integrated form is written with factor 2 in k depending on definition
of rate constant — be consistent with definition.)
Half-life for second order: (t_{1/2} = \dfrac{1}{k[A]_0}) (note dependence on initial concentration).
27. Pseudo-first order reactions — explanation and
hydrolysis example
Answer (long):
When a reaction involves two reactants A and B with rate (r = k[A][B]) but one reactant (say B) is present
in large excess such that [B] constant, the rate simplifies to
[
r = k'[A]\quad\text{where }k' = k[B]_{excess}.
]
Hence the reaction behaves as first-order in A — called pseudo-first-order. This simplification is useful
experimentally to find k by measuring [A] decay as exponential.
Example: Hydrolysis of an ester in large excess water; water concentration ~ 55.5 M essentially constant
pseudo-first-order in ester.
Exam note: Show experimental strategy: hold excess concentration constant to get simple kinetics.
28. Arrhenius equation; physical meaning of activation
energy (E_a)
Answer (long):
Arrhenius equation:
[
k = A e^{-E_a/(RT)},
]
where (k) is rate constant, (A) frequency (pre-exponential) factor, (E_a) activation energy (J·mol ¹), (R) gas
constant, (T) absolute temperature. Taking natural log:
[
\ln k = \ln A - \frac{E_a}{RT}.
]
Plot (\ln k) vs (1/T) yields straight line slope = (-E_a/R) and intercept = (\ln A).
Physical meaning: (E_a) is the minimum energy barrier molecules must overcome to form activated
complex (transition state). A larger (E_a) means rate increases more steeply with temperature.
Frequency factor A: Related to collision frequency and steric factor (orientation probability).
29. Estimate (E_a) if rate doubles from 300 K to 310 K
Answer (detailed arithmetic):
Use Arrhenius form:
[
\ln\left(\frac{k_2}{k_1}\right)=-\frac{E_a}{R}\left(\frac{1}{T_2}-\frac{1}{T_1}\right).
]
Given (k_2/k_1 = 2,\ T_1 = 300\ \mathrm{K},\ T_2 = 310\ \mathrm{K}).
Compute: (\ln 2 = 0.69314718.) Compute (\Delta(1/T)=1/310 - 1/300 = \dfrac{300-310}{300\times310}
= -\dfrac{10}{93000} = -1.075268817\times10^{-4}\ \text{K}^{-1}.) But formula has negative sign, so:
[
0.69314718 = -\frac{E_a}{R}(-1.075268817\times10^{-4}) = \frac{E_a}{R}\times1.075268817\times10^{-4}.
]
Therefore
[
E_a = \frac{0.69314718 \times R}{1.075268817\times10^{-4}}.
]
Use (R = 8.314462618\ \text{J·mol}^{-1}\text{K}^{-1}). Multiply numerator:
(0.69314718 \times 8.314462618 = 5.762313) (approx).
Now divide:
(E_a = 5.762313 / (1.075268817\times10^{-4}) = 5.762313 \times 9300 ) (since 1/(1.07527×10^-4)
9300).
Compute (5.762313\times9300 = 53564.5249\ \text{J·mol}^{-1} \approx 53.56\ \text{kJ·mol}^{-1}).
(\boxed{E_a \approx 5.36\times10^{4}\ \mathrm{J,mol^{-1}} = 53.6\ \mathrm{kJ,mol^{-1}}.})
Exam tip: Show precise steps for (1/T) and units.
30. Collision theory — assumptions and limitations
Answer (long):
Assumptions:
1.
Molecules are hard spheres moving randomly.
2.
Reactions occur when molecules collide with frequency (Z).
3.
Only a fraction of collisions have energy (E_a); this fraction is (e^{-E_a/(RT)}).
4.
Orientation factor (steric factor (p)) accounts for correct alignment.
5.
Rate constant approximated by (k = pZ e^{-E_a/(RT)}).
Limitations:
Over-simplifies molecular interactions (neglects potential energy surfaces).
Does not account for quantum effects (tunneling).
Assumes gas-phase hard-sphere collisions; poorly describes solutions.
Cannot predict pre-exponential factor accurately (steric factors often <<1).
Ignores multi-step mechanisms and activated complex structure — Transition State Theory (TST)
provides more accurate framework.
Conclusion: Useful qualitative tool and sometimes quantitative estimate, but limited for complex/
condensed-phase reactions.
31. Activation energy on energy profile diagram
Answer (long):
Energy profile (reaction coordinate diagram): Vertical axis = potential energy (or Gibbs free energy),
horizontal = reaction coordinate. For exothermic reaction:
Reactants at higher energy than products.
A maximum (transition state/activated complex) between reactants and products.
Activation energy for forward reaction (E_a^{fwd}) is energy difference between reactants and
transition state.
Activation energy for reverse (E_a^{rev}) is difference between products and transition state.
(\Delta H = E_a^{fwd} - E_a^{rev}).
Exam drawing: Label energies clearly, show Ea,fwd and Ea,rev, and H. Discuss how catalyst lowers Ea by
providing alternate lower-energy pathway.
32. Rate-determining step (RDS) in multi-step mechanism
Answer (long):
In a mechanism with several elementary steps, the rate-determining step is the slowest step — it controls
overall reaction rate because subsequent steps cannot proceed faster than the slowest bottleneck. If the RDS
is unimolecular, observed rate law mirrors that elementary step; if more complex, pre-equilibria or steady-
state approximations may be needed to derive observed rate law. Always justify selection of RDS based on
energy profile or experimentally.
Worked idea: For mechanism with fast pre-equilibrium followed by slow RDS, derive overall rate by
expressing intermediate concentrations from pre-equilibrium and substituting into rate law for RDS.
33. Effect of catalysts on rate and equilibrium
Answer (long):
A catalyst provides an alternative reaction pathway with lower activation energy for both forward and
reverse reactions. Consequently:
Reaction rates increase (both forward and reverse).
Time to reach equilibrium reduced.
Equilibrium constant (K) unchanged (thermodynamic property dependent only on temperature).
On energy diagram: catalyst lowers the peak(s) — show on sketch.
Examples: Enzymes in biology accelerate reactions but don't alter G°; heterogeneous catalysts (e.g., Pt) in
hydrogenation.
34. Units of rate constant (k) for different orders
Answer (long):
Zero order: Rate = (k) (mol·L ¹·s ¹) ([k] = \text{mol·L}^{-1}\text{s}^{-1}).
First order: Rate = (k[A]) ([k] = \text{s}^{-1}).
Second order: Rate = (k[A]^2) or (k[A][B]) ([k] = \text{L·mol}^{-1}\text{s}^{-1}).
Third order: ([k] = \text{L}^2\text{mol}^{-2}\text{s}^{-1}).
Exam tip: Always include units for clarity.
35. Determine first-order k from pressure vs time data
(manometry)
Answer (long):
For gaseous first-order reaction with total pressure proportional to concentration, one can use the
integrated law:
[
\ln\frac{P_t}{P_0} = -kt,
]
where (P) is total (or partial) pressure proportional to concentration. Procedure:
1.
Measure pressure at known time intervals.
2.
Plot (\ln P) vs (t); slope = −k.
3.
Use linear regression for best k; report uncertainty.
Example: Decomposition of N(_2)O(_5) in gas phase — measure pressure decrease over time.
36. Chain reaction and example (detailed)
Answer (long):
Chain reaction: reaction proceeds via radical intermediates in steps: initiation (radical generation),
propagation (radicals react producing new radicals), and termination (radicals recombine). Characteristic
features include induction period, chain carriers, and high reactivity.
Example: ( \ce{H2 + Br2 -> 2HBr} ) (radical chain)
Initiation: (\ce{Br2 -> 2Br^.}) (photochemical)
Propagation: (\ce{Br^. + H2 -> HBr + H^.}) ; (\ce{H^. + Br2 -> HBr + Br^.})
Termination: (\ce{Br^. + Br^. -> Br2}), (\ce{H^. + Br^. -> HBr})
Derive rate laws by steady-state assumption for radicals to get experimentally observed rate law (non-
intuitive orders).
37. Fractional order reactions — concept and example
Answer (long):
Fractional order arises when observed rate law has non-integer exponents due to complex mechanisms
(adsorption, surface reactions, chain reactions) or when intermediate steady states produce effective
fractional dependence. Example: certain catalytic reactions show overall order 1.5; enzyme kinetics can
give fractional apparent orders at intermediate substrate concentrations.
Analytical handling: Solve integrated forms numerically or using approximations; discuss physical origin
and experimental detection.
38. Steric factor and its role in frequency factor A
Answer (long):
Steric factor (p) accounts for orientation requirement: only a fraction (p) of collisions that have sufficient
energy have the correct orientation for reaction. Thus (A = pZ), where (Z) is collision frequency calculated
from kinetic gas theory. Typical (p \ll 1) for complex molecules, near 1 for simple atom–atom reactions.
Example: For (\ce{H + Cl2 -> HCl + Cl}) steric factor close to 1; for complex organic reactions it may be
very small.
39. Half-life for second-order reaction (2A ) products
Answer (long):
From integrated form (\dfrac{1}{[A]_t} = \dfrac{1}{[A]_0} + kt). For half-life set ( [A]_t = \dfrac{[A]_0}{2}):
[
\frac{2}{[A]0} = \frac{1}{[A]0} + kt{1/2} \Rightarrow kt{1/2} = \frac{1}{[A]_0}.
]
Therefore
[
\boxed{t_{1/2} = \frac{1}{k[A]_0}}.
]
Note: This half-life decreases with increasing initial concentration (opposite behavior to zero order).
40. First-order reaction with (k=3.0\times10^{-3}\
\mathrm{s^{-1}}) — fraction remaining after 5 min
Answer (calculation):
Given (k = 3.0\times10^{-3}\ \mathrm{s^{-1}}), (t = 5\ \text{min} = 300\ \text{s}).
Fraction remaining (= e^{-kt} = e^{-0.003\times300} = e^{-0.9}).
Compute e^-0.9 0.40656966.
(\boxed{\text{Fraction remaining} \approx 0.4066\ (40.66%)}).
Interpretation: About 59.34% reacted.
Unit III — Electrochemistry (Questions 41–60)
41. Molar conductance (\Lambda_m) and relation to
conductivity
Answer (long):
Definitions:
Specific conductance (conductivity) ( ) (S·cm ¹) is conductance per unit cell length and cross-section:
( = \dfrac{G \cdot l}{A}), where (G) is cell conductance (S), (l) length, (A) area.
Molar conductance (\Lambda_m) (S·cm²·mol ¹) is conductance of an electrolyte solution containing
one mole of electrolyte when placed between electrodes 1 cm apart:
[
\boxed{\Lambda_m = \frac{\kappa \times 1000}{c_{\text{mol·m}^{-3}}}}
]
In convenient units when c in mol·L ¹:
[
\Lambda_m = \frac{\kappa}{c} \quad(\kappa\text{ in S·cm}^{-1},\ c\text{ in mol·cm}^{-3}),
]
but most textbooks use (\Lambda_m = \kappa \times \dfrac{1000}{c\ (\text{mol·L}^{-1})}) adjusting units.
Interpretation: (\Lambda_m) corrects conductivity to per-mole basis; useful to compare ion mobilities
independent of concentration.
42. Variation of (\Lambda_m) with dilution for strong
electrolytes
Answer (long):
For strong electrolytes:
At high concentrations, ionic interactions (inter-ionic attraction, ion pairing) reduce mobility
(\Lambda_m) smaller.
On dilution, these interferences decrease (\Lambda_m) increases gradually, approaching limiting
molar conductance (\Lambda_m^0) as (c\to0).
Kohlrausch’s empirical law for strong electrolytes:
[
\Lambda_m = \Lambda_m^0 - A\sqrt{c}
]
(where A depends on temperature and solvent). Plotting (\Lambda_m) vs (\sqrt{c}) gives straight line
intercepting (\Lambda_m^0).
43. Sharp increase of (\Lambda_m) on dilution for weak
electrolytes
Answer (long):
Weak electrolytes are only partially ionized; on dilution degree of dissociation increases significantly
(Ostwald’s dilution law), producing more ions per formula unit and hence a large increase in measured
conductance. Thus (\Lambda_m) rises steeply with dilution and tends toward (\Lambda_m^0) at infinite
dilution.
Quantitatively: For weak electrolyte HA, degree dissociation (\alpha = \dfrac{\Lambda_m}{\Lambda_m^0}),
linking conductivity and dissociation.
44. Kohlrausch’s law — statement and applications
Answer (long):
Law: At infinite dilution, the molar conductance of an electrolyte equals sum of contributions of its
constituent ions:
[
\boxed{\Lambda_m^0 = \lambda_+^0 + \lambda_-^0}
]
where (\lambda_i^0) is limiting molar ionic conductance of ion i. Applications:
Determination of (\Lambda_m^0) for weak electrolytes by extrapolation of strong-electrolyte data.
Estimation of ionic conductances and mobilities.
Calculating degree of dissociation and (K_a) from conductivity.
Determination of equivalent conductance and ionic contributions for complex ions.
Experimental note: Use measurements at several dilutions and Kohlrausch plot (\Lambda_m) vs (\sqrt{c}).
45. Conductivity calculation example (digits carefully)
Problem: = (1.50\times10^{-3}) S·cm ¹ at c = 0.001 mol·L ¹. Find (\Lambda_m) in S·cm²·mol ¹.
Solution (careful units):
Convert c to mol·cm ³: (0.001\ \text{mol·L}^{-1} = 0.001\ \text{mol·dm}^{-3} = 0.001\
\text{mol·1000 cm}^{-3} = 1.0\times10^{-6}\ \text{mol·cm}^{-3}). (Because 1 L = 1000 cm³.)
Use (\Lambda_m = \dfrac{\kappa}{c}) with in S·cm ¹ and c in mol·cm ³:
[
\Lambda_m = \frac{1.50\times10^{-3}}{1.0\times10^{-6}} = 1.50\times10^{3}\ \text{S·cm}^2\text{·mol}^{-1}.
]
(\boxed{\Lambda_m = 1.50\times10^{3}\ \mathrm{S\ cm^2\ mol^{-1}}}).
Note: Often expressed in S·cm²·eq ¹ for equivalent conductance or converted to S·m²·mol ¹ in SI.
46. Transport number definition and determination
methods
Answer (long):
Definition: Transport number (t_i) for ion i is the fraction of total current carried by that ion in an
electrolyte:
[
t_i = \frac{I_i}{I_{total}}.
]
Properties: (t_+ + t_- = 1) for binary electrolytes.
Determination methods:
1.
Hittorf method: Pass known charge through electrolyte for time t; measure concentration changes in
compartments adjacent to electrodes; calculate t based on amount of ion transported relative to charge
passed.
2.
Moving boundary method: Use a junction between solutions of different electrolytes; upon passing
current, boundary moves; measure velocity and compute transport numbers from boundary
displacement and current.
Exam detail: For Hittorf show basic equation: (t_+ = \dfrac{z_- \Delta n_- F}{Q}) etc where n measured
concentration change, Q = total charge.
47. Hittorf method principle (concise with steps)
Answer (long):
Principle: Passing an electric current causes ions to migrate: cations toward cathode, anions toward anode.
The Hittorf method measures the change in concentration of ions in compartments next to the electrodes
after current passage. The change in moles of an ion is proportional to the net charge transported by the
other ion; using Faraday’s law and mass balance one computes transport numbers.
Procedure highlights:
1.
Fill conductivity cell with electrolyte, isolate compartments.
2.
Measure initial concentrations in each compartment.
3.
Pass current for known time.
4.
Measure final concentrations near electrodes.
5.
Use measured concentration changes to compute t_+ and t_-.
Key formula (conceptual): Transport number (t_+ = \dfrac{z_- \Delta n_- F}{I t}) (details depend on sign
conventions).
48. Limiting molar conductance (\Lambda_m^0) —
meaning
Answer (long):
(\Lambda_m^0) (or (\Lambda_\infty)) is the molar conductance at infinite dilution where inter-ionic
interactions are negligible and ions move freely. It is characteristic of the ions and temperature. It enables
decomposition into individual ionic contributions via Kohlrausch’s law: (\Lambda_m^0 = \lambda_+^0 +
\lambda_-^0).
Practical use: Determine (\Lambda_m^0) by extrapolating (\Lambda_m) vs (\sqrt{c}) plot to c = 0.
49. Ostwald’s dilution law for weak electrolytes
Answer (long):
For weak electrolyte (HA \leftrightarrow H^+ + A^-), degree dissociation (\alpha), initial concentration (c):
[
K_a = \frac{[H^+][A^-]}{[HA]} = \frac{(c\alpha)(c\alpha)}{c(1-\alpha)} = \frac{c\alpha^2}{1-\alpha}.
]
This is Ostwald’s dilution law. For small (~dilute), approximate (1-\alpha\approx 1) (K_a \approx c
\alpha^2) (\alpha \approx \sqrt{K_a/c}).
Exam remark: Use alongside conductivity data with (\alpha = \Lambda_m/\Lambda_m^0) to determine
(K_a).
50. Compute (K_a) for weak electrolyte with c=0.01 M, =
0.1
Answer (calculation): Use exact formula:
[
K_a = \frac{c\alpha^2}{1-\alpha} = \frac{0.01 \times (0.1)^2}{1-0.1} = \frac{0.01 \times 0.01}{0.9} =
\frac{1.0\times10^{-4}}{0.9} = 1.111\ldots\times10^{-4}.
]
(\boxed{K_a = 1.11\times10^{-4}}).
Show arithmetic steps in exams: compute numerator and divide carefully.
51. Degree of dissociation from conductance data —
method & formula
Answer (long):
For weak electrolyte, measured molar conductance (\Lambda_m) at concentration c and limiting molar
conductance (\Lambda_m^0):
[
\alpha = \frac{\Lambda_m}{\Lambda_m^0}.
]
This follows since (\Lambda_m = \alpha\Lambda_m^0) (only fraction of molecules ionized contributing
to conductance), ignoring mobility changes with concentration. Once known, use Ostwald’s law to
compute (K_a):
[
K_a = \frac{c\alpha^2}{1-\alpha}.
]
Experimental steps:
1.
Measure conductance at given c, obtain .
2.
Compute (\Lambda_m = \kappa \times 1000 / c) (ensure consistent units).
3.
Estimate (\Lambda_m^0) by extrapolation from strong electrolyte data or literature.
4.
Compute and then K_a.
Limitations: Applies in dilute regime; activity corrections needed at higher ionic strength.
52. Hydrolysis of salts — definition and acidic salt example
Answer (long):
Hydrolysis: Reaction of ions with water to produce H(^+) or OH(^-) altering pH. Depends on strengths of
parent acid/base.
Acidic salt example: ( \ce{NH4Cl} ) in water:
( \ce{NH4+ + H2O <=> NH3 + H3O+} ) (ammonium hydrolyzes producing H(_3)O(^+) solution
acidic).
Hydrolysis constant (K_h = \dfrac{[NH_3][H_3O^+]}{[NH_4^+]}). Relate to (K_a) of NH(_4^+) or via
(K_b) of conjugate base.
Quantitative relation: For salt of weak base BH :
[
K_h = \frac{K_a K_b}{?} \quad\text{(derive using water autoionization and Ka/Kb relations)}.
]
Simpler: For conjugate pair HA/A , (K_a K_b = K_w).
pH estimation: For salt of weak base (e.g., NH(_4)Cl), approximate ( [H^+] = \sqrt{K_a c} ) with (K_a =
K_w/K_b) of conjugate base.
53. pH of 0.01 M sodium acetate (detailed calc)
Given: (K_a(\text{acetic}) = 1.8\times10^{-5}), (K_w = 1.0\times10^{-14}). For acetate salt (\ce{CH3COO^-}),
its base constant (K_b = K_w/K_a = 1.0\times10^{-14} / 1.8\times10^{-5} = 5.555\ldots\times10^{-10}).
Hydrolysis reaction: (\ce{A^- + H2O <=> HA + OH^-}). For c = 0.01 M, let (x=[OH^-]) at equilibrium. For
small x,
[
K_b = \frac{x^2}{c - x} \approx \frac{x^2}{c}.
]
So (x = \sqrt{K_b c}).
Compute:
(K_b c = 5.555\ldots\times10^{-10} \times 0.01 = 5.555\ldots\times10^{-12}).
(\sqrt{5.555\ldots\times10^{-12}} = \sqrt{5.555\ldots}\times10^{-6} \approx 2.3570\times10^{-6}\
\text{M}).
So ([OH^-] = 2.357\times10^{-6}) M. Then (pOH = -\log_{10}(2.357\times10^{-6})).
Compute pOH:
(\log_{10}(2.357) \approx 0.372).
(-\log_{10}(2.357\times10^{-6}) = 6 - 0.372 = 5.628).
So (pOH \approx 5.628). Thus (pH = 14 - 5.628 = 8.372).
(\boxed{pH \approx 8.37}).
Check approximations: x c (2.36×10 ⁶ 0.01) so approximation valid.
54. Theory of acid-base indicators (detailed)
Answer (long):
Indicators are weak acids (or bases) with distinct colors for protonated and deprotonated forms:
[
\ce{HIn <=> H+ + In^-}
]
Equilibrium constant (K_{In} = \dfrac{[H^+][In^-]}{[HIn]}). Rearranged:
[
\frac{[In^-]}{[HIn]} = 10^{\mathrm{pH} - \mathrm{p}K_{In}}.
]
Color change occurs when ratio (\dfrac{[In^-]}{[HIn]}) varies through values where two colored forms are in
comparable concentrations (approx 1:10 to 10:1). Hence visible range pK_in ± 1. At pH = pK_in, both
forms are in equal concentration and usually an intermediate color is observed.
Example: Phenolphthalein pKa 9.3; colorless below ~8.2 and pink above ~10.0. Methyl orange pKa
3.5.
55. Ionic strength effect on activity coefficients (qualitative)
Answer (long):
Ionic strength (I = \frac{1}{2}\sum c_i z_i^2) quantifies total ionic environment. As ionic strength
increases:
Electrostatic interactions between ions are screened (Debye-Hückel theory).
Activity coefficients ( _i) decrease ( < 1), meaning effective activities are smaller than concentrations.
Equilibrium constants expressed in terms of activities remain constant, but concentration-based
equilibrium constants appear to shift with ionic strength.
For dilute solutions, Debye–Hückel limiting law approximates (\log_{10} _i = -A z_i^2 \sqrt{I}) (A
depends on T and solvent).
Implication: For precise equilibrium work (e.g., pKa determination), correct concentrations to activities or
keep ionic strength constant via supporting electrolyte.
56. Conductance cell problem (detailed with resolution of
potential conflict)
Problem variant: Given (specific conductance) and cell constant, compute conductance and current at 1
V.
Given: = (4.0\times10^{-4}) S·cm ¹, cell constant = 1.25 cm ¹. (Note earlier 250 was inconsistent;
ignore that). Compute:
Conductance (G = \times (\text{cell constant}) = 4.0\times10^{-4}\ \text{S·cm}^{-1}\times1.25\
\text{cm}^{-1} = 5.0\times10^{-4}\ \text{S}.)
Resistance (R = 1/G = 1/(5.0\times10^{-4}) = 2000\ \Omega.)
Current at 1 V: (I = V/R = 1/2000 = 5.0\times10^{-4}\ \text{A} = 0.50\ \text{mA}.)
(\boxed{G = 5.0\times10^{-4}\ \mathrm{S},; I=0.50\ \mathrm{mA}}).
Exam practice: Always reconcile given data; if multiple resistance figures provided, choose consistent
route.
57. Transport numbers for H and OH — typical values
and reasons
Answer (long):
H(^+) and OH(^-) have exceptionally high ionic mobilities due to the Grotthuss proton-hop mechanism.
Typical transport numbers in aqueous solutions depend on counterion and concentration but often:
(t_{H^+} \approx 0.8)–0.95 (varies with electrolyte).
(t_{OH^-} \approx 0.45)–0.9 depending on medium and concentration.
Reason: Proton transfer mechanism allows rapid migration relative to other ions; similarly OH migrates
efficiently. These high values imply much of the current carried by H /OH in acid/base solutions.
Exam note: Provide approximate ranges and physical reasoning; exact numbers require experimental
determination.
58. Experimental determination of (\Lambda_m^0) for
weak electrolyte
Answer (long):
Method: Measure (\Lambda_m) at several low concentrations (ideally spanning orders of magnitude). For
weak electrolytes, direct measurement of very dilute solutions may be imprecise; instead use Kohlrausch’s
approach:
1.
Measure (\Lambda_m) vs (\sqrt{c}) for a series of dilutions.
2.
Extrapolate linear portion to (c \to 0) (or (\sqrt{c} \to 0)).
3.
The intercept gives (\Lambda_m^0).
Alternatively combine partial molar contributions from strong electrolytes when ionic contributions
known.
Practical notes: Temperature must be controlled; cell constant calibrated; conductance readings corrected
for solvent conductivity.
59. Relationship (K_a K_b = K_w) — derivation
Answer (long):
For conjugate acid–base pair ( \ce{HA <=> H+ + A^-}) with (K_a = \dfrac{[H^+][A^-]}{[HA]}), and ( \ce{B +
H2O <=> BH+ + OH-}) with (K_b = \dfrac{[BH^+][OH^-]}{[B]}). For conjugate pair A and HA, relation
between (K_a) (for HA) and (K_b) (for A ) follows from water autoprotolysis (K_w = [H^+][OH^-]):
[
K_a K_b = \left(\frac{[H^+][A^-]}{[HA]}\right)\left(\frac{[BH^+][OH^-]}{[B]}\right) \quad\text{(for appropriate
conjugates)},
]
but simplest derivation for conjugate pair HA/A :
[
K_a (\text{HA}) \times K_b (\text{A}^-) = \frac{[H^+][A^-]}{[HA]} \times \frac{[HA][OH^-]}{[A^-]} = [H^+]
[OH^-] = K_w.
]
Hence
[
\boxed{K_a K_b = K_w.}
]
60. Three applications of conductance measurements
(detailed)
Answer (long):
1.
Determination of (K_a) of weak acids / degree of dissociation: Measure molar conductance vs
concentration and extrapolate to infinite dilution to find (\Lambda_m^0), then compute dissociation
and hence (K_a) via Ostwald’s law.
2.
Conductometric titrations: Useful for analyzing titrations where species change ionic nature (e.g.,
titration of strong acid with strong base: conductivity minimum at equivalence). Widely used when
visual indicators unsuitable (colored or complex solutions).
3.
Solubility and ionic mobility determinations: Determine solubility of sparingly soluble salts from
conductivity of saturated solution; estimate ionic mobilities and transport numbers (moving boundary)
which are valuable in electrochemical engineering and battery research.
Further uses: Detection of end point in precipitation titrations, assessment of electrolyte purity, and
monitoring reaction progress in ionic reactions.