Chemical Reaction Engineering

Rate laws

Use this for “E = 80 kJ/mol and k = 0.05 per min at 300 K. Find k at 320 K”, or for E from k at two temperatures.

Diagram

−4−2033.13.23.33.4ln k (k in min⁻¹)T₂ = 320 KT₁ = 300 Kslope = −Eₐ/R = −9,620 K1000 ÷ T (K⁻¹)
ln
k
against
1
T
is
straight:
ln
k
=
ln
A
−
Eₐ/(RT).
Its
slope
through
the
two
readings
is
ln(k₂ ÷ k₁)
1
T₂
−
1
T₁
=
−9,620
K.
Eₐ = −R × slope = 8.314 J/(mol·K) × 9,620 K = 80 kJ/mol.
This is an example. Type your own values to start a new problem.
ln(
k₂ (min⁻¹)
÷
k₁ (min⁻¹)
)
=
E (kJ/mol)
÷
R
×
(1
÷
T₁ (K)
−
1
÷
T₂ (K)
)
r
Ratio k₂ ÷ k₁
calculated

Formulas

r
=
k₂
k₁
7.424
=
0.3712
0.05
ln(
r
)
=
E
8.314
×
(
1
T₁
−
1
T₂
)
ln(7.424)
=
80,000
8.314
×
(
1
300
−
1
320
)
Formulas are worked in J/mol. The step-by-step shows the conversions.

Assumptions

•
E and the pre-exponential factor A stay the same between the two temperatures.
•
Temperatures are in kelvins (°C + 273.15); R = 8.314 J/(mol·K), so E is worked in J/mol.
•
k₁ and k₂ share one unit; only their ratio sets E, whatever the order.
•
The “k doubles every 10 K” rule is rough: it holds only near one E and T.

Step-by-step

WE KNOW
E = 80 kJ/mol, k₁ = 0.05 min⁻¹, T₁ = 300 K, T₂ = 320 K
FIND
ratio k₂ ÷ k₁ (r), rate constant at T₂ (k₂)
Step 1 · Convert to the formula’s units
The formulas don’t work directly in the units you chose, so convert first (to J/mol).
E = 80 kJ/mol = 80,000 J/mol (1 kJ/mol = 1000 J/mol)
Step 2 · Find ratio k₂ ÷ k₁ (r)
Use ln(r) = E ÷ 8.314 × (1 ÷ T₁ − 1 ÷ T₂)
Divide
k
=
A
e
−
E
÷ RT
at
T₂
by
k
at
T₁
:
A
cancels,
leaving
e
raised
to
(
E
R
)(
1
T₁
−
1
T₂
).
r
=
e^(
E
÷
8.314
×
(
1
T₁
−
1
T₂
))
r
=
e^(80,000
÷
8.314
×
(
1
300
−
1
320
))
r
=
e
80,000 ÷ 8.314 × (0.00333333 − 0.003125)
r
=
e
80,000 ÷ 8.314 × 0.00020833
r
=
e
9,622.32 × 0.00020833
r
=
e
2.00462
r
=
7.424
Step 3 · Find rate constant at T₂ (k₂)
Use r = k₂ ÷ k₁
Scale
k₁
by
how
many
times
faster
the
reaction
runs.
k₂
=
r
×
k₁
k₂
=
7.424
×
0.05
k₂
=
0.3712
min⁻¹
Check
Put the numbers back in. Both sides should match.
7.424
=
0.3712
0.05
✓
ln(7.424)
=
80,000
8.314
×
(
1
300
−
1
320
)
✓
Topic check
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