આ MCQ મોડ્યુલ આના પર આધારિત છે: Half Life Pseudo
Half Life Pseudo
આ મૂલ્યાંકન આના પર આધારિત હશે: Half Life Pseudo
મૂલ્યાંકન બનાવવામાં તેમની સામગ્રી સામેલ કરવા ચિત્રો, PDF અથવા Word દસ્તાવેજ અપલોડ કરો.
Half Life Pseudo
3.6 First Order Gas-Phase Reactions and Partial Pressures
For a gas-phase reaction \( A(g) \to B(g) + C(g)\) the concentration of A is proportional to its partial pressure \(p_A\). Suppose initially only A is present at total pressure \(p_i\). At time \(t\), \(p_A\) drops by an amount \(x\); pressure of B and C each rise by \(x\). The total pressure is
So \( p_A = p_i - x = p_i - (p_t - p_i) = 2p_i - p_t \). Substituting in the first-order equation
The thermal decomposition of \(N_2O_5(g)\) is first order: \(2 N_2O_5(g) \to 2 N_2O_4(g) + O_2(g)\). At constant volume and temperature, the following data were measured for an analogous reaction \(N_2O_5 \to 2NO_2 + ½ O_2\) starting at \(p_i\):
| Time / s | Total pressure / atm |
|---|---|
| 0 | 0.5 |
| 100 | 0.512 |
Calculate the rate constant.
Using \(p_A = 2p_i - p_t = 2(0.5) - 0.512 = 0.488\) atm? — careful: stoichiometry here gives 2.5 mol gas per 1 mol reactant.
Using NCERT formula derived for \(2N_2O_5 \to 2N_2O_4 + O_2\): \( p_{A} = p_i - 2(p_t-p_i)\). With \(p_i = 0.5, p_t = 0.512\):
\(p_A = 0.5 - 2(0.012) = 0.476\) atm.
\(k = \dfrac{2.303}{100}\log\dfrac{0.5}{0.476} = \dfrac{2.303}{100}(0.0216) = 4.98 \times 10^{-4}\) s⁻¹.
3.7 Half-Life of a Reaction
The half-life of a reaction, denoted \(t_{1/2}\), is the time required for the concentration of a reactant to fall to half of its initial value.
Half-Life of a Zero Order Reaction
For zero order: \([R] = [R]_0 - kt\). Setting \([R] = [R]_0/2\) at \(t = t_{1/2}\):
For zero order, \(t_{1/2}\) is directly proportional to the initial concentration.
Half-Life of a First Order Reaction
For first order: \(k = \dfrac{2.303}{t}\log\dfrac{[R]_0}{[R]}\). Setting \([R] = [R]_0/2\) at \(t = t_{1/2}\):
For first order, \(t_{1/2}\) is constant — independent of starting concentration. This is why radioactive nuclei have a single quoted half-life.
Summary of Integrated Rate Equations
| Order | Rate Law | Integrated form | Linear plot | Slope | t₁/₂ | Units of k |
|---|---|---|---|---|---|---|
| 0 | Rate = k | [R] = [R]₀ − kt | [R] vs t | −k | [R]₀/2k | mol L⁻¹ s⁻¹ |
| 1 | Rate = k[R] | ln[R] = ln[R]₀ − kt | ln[R] vs t | −k | 0.693/k | s⁻¹ |
A first-order reaction is found to have a rate constant \(k = 5.5 \times 10^{-14}\) s⁻¹. Find the half-life of the reaction.
\(t_{1/2} = \dfrac{0.693}{k} = \dfrac{0.693}{5.5 \times 10^{-14}\text{ s}^{-1}} = 1.26 \times 10^{13}\) s.
Show that for a first-order reaction the time required for 99% completion is twice the time required for 90% completion.
For 99% completion: \([R]/[R]_0 = 0.01\). Then \(t_{99} = \dfrac{2.303}{k}\log\dfrac{1}{0.01} = \dfrac{2.303}{k}(2) = \dfrac{4.606}{k}\).
For 90% completion: \([R]/[R]_0 = 0.10\). Then \(t_{90} = \dfrac{2.303}{k}\log\dfrac{1}{0.10} = \dfrac{2.303}{k}(1) = \dfrac{2.303}{k}\).
Therefore \(t_{99}/t_{90} = 4.606/2.303 = 2\). Hence \( t_{99} = 2 \, t_{90}\). Q.E.D.
The half-life for radioactive decay of \(^{14}C\) is 5730 years. An archaeological artefact contains wood that has only 80% of the \(^{14}C\) found in a living tree. Estimate the age of the sample.
For first order decay, \(k = 0.693/t_{1/2} = 0.693/5730 = 1.21 \times 10^{-4}\) yr⁻¹.
Time taken for [R]/[R]₀ to fall to 0.80:
\(t = \dfrac{2.303}{k}\log\dfrac{1}{0.80} = \dfrac{2.303}{1.21 \times 10^{-4}}(0.0969) = 1845\) years.
The sample is approximately 1845 years old.
Interactive: Half-Life Visualizer (First Order)
Watch a population of reactant atoms decay through successive half-lives.
Number of half-lives elapsed = 2.0
Fraction of [R] remaining = 0.250 (= 25.0%)
Rate constant k = 0.00693 s⁻¹
3.8 Pseudo First Order Reactions
Reactions that look like they should be of higher order but turn out to follow first-order kinetics under certain conditions are called pseudo first order reactions.
Hydrolysis of Ester
Consider \( CH_3COOC_2H_5 + H_2O \to CH_3COOH + C_2H_5OH\). The true rate law would be Rate = \(k\,[CH_3COOC_2H_5][H_2O]\) (overall order 2). However, when carried out in dilute aqueous solution, water is in vast excess:
- [Ester] ≈ 0.01 M
- [H₂O] ≈ 55.5 M (almost pure water)
The change in \([H_2O]\) during the entire reaction is negligible — perhaps 0.01 M out of 55.5 M, i.e. 0.018%. So [H₂O] is treated as a constant:
This is now a first order rate law in ester, with a pseudo first order rate constant \(k'\).
Inversion of Cane Sugar
Another classic example:
(sucrose hydrolysing to glucose + fructose). Again [H₂O] is enormously in excess. The reaction follows first-order kinetics with a half-life independent of sucrose concentration.
| Time / min | [Sucrose]/mol L⁻¹ |
|---|---|
| 0 | 0.500 |
| 30 | 0.451 |
| 60 | 0.407 |
| 90 | 0.367 |
Plotting \(\log[\text{sucrose}]\) against time gives a straight line, confirming pseudo first order kinetics.
Setup: Take 25 mL of 1.0 M sucrose solution and 25 mL of 1.0 M HCl. Mix and immediately use a polarimeter to measure the angle of optical rotation at intervals of 10 min for one hour. Sucrose rotates plane-polarised light to the right (+); the products (glucose + fructose, 'invert sugar') rotate to the left (−). Compute \(\log(r_t - r_\infty)\) where \(r\) is the rotation.
You will obtain a straight line with negative slope. Slope = \(-k/2.303\) gives the pseudo first order rate constant directly. Since [H₂O] is virtually constant (~55 M against ~0.5 M sugar), the apparent first-order behaviour is observed even though the molecular act involves both sugar and water.
Historically this experiment by Wilhelmy in 1850 was the very first quantitative kinetic study and gave birth to chemical kinetics as a discipline.
Interactive: Why Water in Excess Means First Order
Drag the slider for the [water]:[ester] ratio and see how the pseudo rate constant \(k' = k[H_2O]\) and the % change in [water] during the reaction respond.
If 100% of ester reacts, fractional change in [H₂O] = 0.018 %
Verdict: [H₂O] is essentially constant → reaction follows first order kinetics in ester.
Hydrolysis of methyl acetate in aqueous solution has been studied by titrating the liberated acetic acid against sodium hydroxide. The volume of NaOH at infinite time is 17.4 mL. At time t the volume used was 10.6 mL after 25 min. Calculate the pseudo first order rate constant.
NaOH volume at \(t = \infty\) corresponds to total ester originally present, i.e. \([R]_0 \propto V_\infty = 17.4\) mL.
NaOH volume at time t corresponds to ester reacted, so unreacted ester \([R] \propto (V_\infty - V_t) = 17.4 - 10.6 = 6.8\) mL.
\(k' = \dfrac{2.303}{t}\log\dfrac{V_\infty}{V_\infty - V_t} = \dfrac{2.303}{25}\log\dfrac{17.4}{6.8}\)
\(= \dfrac{2.303}{25}(0.4079) = 0.0376\) min⁻¹.
Competency-Based Questions
Q1. The half-life of a first order reaction is 30 min. The fraction of reactant remaining after 90 min is: L3
Q2. For a zero order reaction with k = 0.020 mol L⁻¹ min⁻¹ and [R]₀ = 0.20 mol L⁻¹, the half-life is: L3
Q3. (Short answer) Why is the hydrolysis of cane sugar in dilute aqueous acid called pseudo first order? L4
Q4. (True/False) The half-life of a first order reaction increases as initial concentration increases. L2
Q5. (Long answer) A radioactive isotope has a half-life of 10 days. What percentage will remain undecayed after 30 days, and how long will it take for only 10% to remain? L5
For 10% remaining: \(k = 0.693/10 = 0.0693\) day⁻¹. \(t = (2.303/k)\log(100/10) = (2.303/0.0693) \times 1 = 33.2\) days.
Assertion–Reason Questions
(A) Both true & R explains A. (B) Both true but R does not explain A. (C) A true, R false. (D) A false, R true.
Assertion: The half-life of a first order reaction is independent of initial concentration.
Reason: Half-life depends only on the rate constant which is itself temperature-dependent only.
Assertion: Hydrolysis of an ester in dilute aqueous solution is pseudo first order.
Reason: Esters react with water in a 1:1 stoichiometry.
Assertion: For a zero order reaction half-life increases linearly with initial concentration.
Reason: \(t_{1/2} = [R]_0/2k\).
Frequently Asked Questions - Half Life Pseudo
What is the main concept covered in Half Life Pseudo?
How is Half Life Pseudo useful in real-life or applied chemistry?
What are the key reactions students should memorize for Half Life Pseudo?
How does this part connect to other parts of Chapter 3?
What types of CBSE board questions come from Half Life Pseudo?
How can students use the interactive simulation effectively?
🎯 Chemistry ની પ્રેક્ટિસ કરો
તમે જે ભણ્યા તેનું પૂરું પેપર આપો, પ્રશ્ન દીઠ તપાસાયેલું.