General Chemistry II
Problem set #3
1. For the reaction: 4A(g) + 3B(g) 🡪 2C(g) the following data were obtained at constant temperature.
a. What is the order with respect to each
reactant?
b. Write the rate law.
c. Calculate k (using the data from Expt. 1).
Rate = k[A]a[B]b; Look at experiment 2 and 4
a = order with respect to A, - same [A] but double [B]
b = order with respect to B, -> we can neglect [A] as it doesn’t change
k = rate const
- initial rate also double
-> rate constant is positive k>0
The rate law of this reaction
Rate = k[A]2 [B]1 => Rate = k[B]b
=> Rate2 / Rate4 = ([B]2 / [B]4)b
We calculate k by => 45/90 = (½)b
substituting the data from
=> ½ = (½)b
experiment
=> b = 1 = order of reaction with respect to B
k = Rate / ([A]2 [B]1)
= 5 / (0.12 *0.1) = 5000
L/mol*min Look at experiment 1 and 2
- same [B] but triple [A]
-> we can neglect [B] as it doesn’t change
- initial rate increase by a factor of 9
->rate constant is positive k>0
=> Rate = k[A]a
=> Rate2 / Rate1 = ([B]2 / [B]1)a
=> 45/5 = (1/3)a
=> 1/9 = (1/3)a
=> a = 2 = order of reaction with respect to A
2. The rate law for the reaction 2NOBr(g) 🡪 2 NO(g) + Br2(g) at some temperature is
a. If the half-life for this reaction is 2.00 s when [NOBr]0 = 0.900 M, calculate the value of k for this
reaction.
b. How much time is required for the concentration of NOBr to decrease to 0.100 M?
Look that rate law of the reaction -> this is a 2nd order reaction
The integrated rate law for 2nd order reactions: 1/[A] = kt + 1/[A]0
[A]0 = initial concentration
[A] = concentration at the time (t)
With the half life: t1/2 = 1/(k[A]0)
=> k = 1/(t1/2[A]0)
k = 1/(2*0.9) = 5/9 L/mol*s
We have: 1/[A] = kt + 1/[A]0
Time required for NOBr to reach 0.1M
t = (1/[A] - 1/[A]0)/k = (1/0.1 - 1/0.9)/(1/(2*0.9)) = 16s
3. The reaction
(CH3)3CBr + OH- 🡪 (CH3)3COH + Br
in a certain solvent is first order with respect to (CH 3)3CBr and zero order with respect to OH-. In
several experiments, the rate constant k was determined at different temperatures. A plot of ln(k)
versus 1/T was constructed resulting in a straight line with a slope value of -1.10 × 10 4 K and a y-
intercept of 33.5. Assume k has units of s-1.
a. Determine the activation energy for this reaction.
b. Determine the value of the frequency factor A.
c. Calculate the value of k at 25 oC.
General Chemistry II
We know some stuff about k (rate const) Use log to get things down on the ground
We need to know Ea (activation energy) ln(k) = ln(A * e^(-Ea/RT))
-> Arrhenius equation: k = A * e^(-Ea/RT) ln(k) = lnA + (-Ea/RT)
A - frequency factor (same unit as k) A plot of ln(k) versus 1/T = a straight line with a slope
R - gas const = 8.314 J/mol*K value of -1.10 × 104 K and y-intercept of 33.5.
T - temperature in Kelvin ln(k) = (-Ea/R)*(1/T) + lnA
=> lnA = 33.5 => A = 3.54*10^14 s-1
25oC = 298 K => Ea/R = 1.10*10^4
=> Ea = 1.10*10^4 * 8.314 = 91454 J/mol
At 25oC.
k = 3.54*10^14 * e^(-91454/(8.314*298)) = 0.0329 s-1
4. For the reaction ABC + D ⇌ AB + CD, ΔHorxn = -55 kJ/mol and Ea(fwd) = 215 kJ/mol.
Assuming a one-step reaction,
a. draw a reaction energy diagram;
b. calculate Ea(rev); rev = reverse reaction
c. sketch a possible transition state if ABC is V-shaped.
We have: ΔHorxn = Ea(fwd) - Ea(rev)
=> Ea(rev) = Ea(fwd) - ΔHorxn = 215 + 55 = 270 kJ/mol
A possible transition state could be A-B-C-D
ABC + D -> ABCD -> AB + CD
And if ABC is V shape
