BSMLS I - MT Chemical Kinetics 1

CHEMICAL KINETICS
Antonio G. Celajes Jr., RCh

WCC PRAYER
LAST WEEK’S LEARNING OBJECTIVES
At the end of the lesson, the students will be able to produce solutions with correct concentration and use it to analyze acids, bases and other solutions.
Introduction to Analytical Chemistry
a. Qualitative versus Quantitative Chemistry
Solutions, Colloids, Acids and Bases
a. Types of Solution and Colloids
b. Factors that affect solubility
c. Electrolytes and Non-electrolytes

d. Methods of expressing concentration of solutions
e. Determination of concentrations of solution
f. The Colligative properties of solution

g. Acids and Bases
Stoichiometry
a. Computations based on balanced equations

TODAY’S LEARNING OBJECTIVES
At the end of the lesson, the students will be able to distinguish every aspect of chemical reactions and
apply it laboratory settings.
Chemical Kinetics
a. Reaction Rates
b. Factors Affecting Reaction Rate
c. Concentration and Rate
d. The Change of Concentration with Time
e. Temperature and Rates
f. Reaction Mechanisms
g. Catalysis
CHEMICAL KINETICS
- studies the rate at which a chemical process occurs; area of chemistry dealing with
speeds/rates of reactions
- besides information about the speed at which reactions occur, kinetics also sheds light
on the reaction mechanism (exactly how the reaction occurs);
Reaction Rates - How we measure rates.
Rate Laws - How the rate depends on amounts of reactants.
Integrated Rate Laws - How to calculate amount left or time to reach a given
amount.
Half-life - How long it takes to react 50% of reactants.
Arrhenius Equation - How rate constant changes with temperature.
Mechanisms - Link between rate and molecular scale processes.
CHEMICAL KINETICS
Rates of reactions can be determined by monitoring the change in concentration of either
reactants or products as a function of time t.
[A] = concentration of reactant A
For the reaction A → B there are two ways of measuring rate:

(1) the speed at which the reactants disappear
(2) the speed at which the products appear
Reactions are reversible, so as products accumulate they can begin to turn back into reactants.
CHEMICAL KINETICS
Early on the rate will depend on only the amount of reactants present. We want to measure the
reactants as soon as they are mixed.
The most useful (and general) way of measuring the rate of the reaction is in terms of change in
concentration per unit time
Rate = ∆[A]/∆t
Most Common Units… Rate = M/s
Where Molarity (M) = moles/Liter
CHEMICAL KINETICS
Reaction rate is the change in the concentration of a reactant or a product with time (M/s).
A → B
rate = -Δ[A] / Δt
rate = Δ[B] / Δt
Δ[A] = change in concentration of A over time period Δt

Δ[B] = change in concentration of B over time period Δt
Because [A] decreases with time, Δ[A] is negative.
CHEMICAL KINETICS
Factors that Affect the Reaction Rate Constant
1. Temperature: At higher temperatures, reactant molecules have more kinetic energy,
move faster, and collide more often and with greater energy
• Collision Theory: When two chemicals react, their molecules have to collide with
each other with sufficient energy for the reaction to take place.
• Kinetic Theory: Increasing temperature means the molecules move faster.
2. Concentrations of reactants
• As the concentration of reactants increases, so does the likelihood that reactant
molecules will collide.
3. Catalysts
• Speed up reactions by lowering activation energy
CHEMICAL KINETICS
Factors that Affect the Reaction Rate Constant
4. Surface area of a solid reactant
• Bread and Butter theory: more area for reactants to be in contact
5. Pressure of gaseous reactants or products
• Increased number of collisions
CHEMICAL KINETICS
Concentration Affects Reaction Rate Constant
Another way of looking at reaction rates…
2N2O5 → 4NO2 + O2
1/2 1/4 1/1 or 1
Notice that for every 1 mole of O2 that appears, 4x as many moles of NO2 will also appear;
In the meantime, twice as many moles of N2O5 will be disappearing as moles of O2 forming;
Changes in concentrations of the reactants and/or products is inversely proportional to their

stoichiometric proportions.
CHEMICAL KINETICS
This means that the rate of the reaction could be written like this…
Rate = −½ ∆ [N2O5]/∆t
Rate = ¼ ∆[NO2]/∆t
Rate = ∆[O2]/∆t
In general, for the reaction: aA + bB → cC + dD
−1 ∆[A] −1 ∆[B] 1 ∆[C] 1 ∆[D]

Rate A = ------------ Rate B = ------------ Rate C = ------------ Rate D = ------------
a ∆t b ∆t c ∆t d ∆t
CHEMICAL KINETICS
1. Neutralization of phosphoric acid (H3PO4) using stannic hydroxide [Sn(OH)4] produces stannic
phosphate [Sn3(PO4)4] and water.
a. Write the correct rate of reaction formula of all reactants and products.
b. At the beginning, 12.24 moles/liter of phosphoric acid was present, determine the
rate of phosphoric acid consumption in M/sec if after 3.76 minutes there is only 7.68
mole/liter phosphoric acid present.
c. What would be the rate of formation in M/min of stannic phosphate if after 2hours
and 21minutes, 43.45grams of it was formed in a 654mL solution?
Sn = 119; P = 31; O = 16; H = 1
CHEMICAL KINETICS
1. Neutralization of phosphoric acid (H3PO4) using stannic hydroxide [Sn(OH)4] produces stannic
phosphate [Sn3(PO4)4] and water.
a. Write the correct rate of reaction formula of all reactants and products.
4H3PO4 + 3Sn(OH)4 → Sn3(PO4)4 + 12 H2O
b. At the beginning, 12.24 moles/liter of phosphoric acid was present, determine the rate
of phosphoric acid consumption in M/sec if after 3.76 minutes there is only 7.68 mole/liter
phosphoric acid present.
I. Given: T1 = 0 sec Ci = 12.24M H3PO4 Tf = 3.76 min = 225.6 sec Cf = 7.68M
II. Required: Rate of H3PO4
CHEMICAL KINETICS
4H3PO4 + 3Sn(OH)4 → Sn3(PO4)4 + 12 H2O
b. At the beginning, 12.24 moles/liter of phosphoric acid was present, determine the rate
of phosphoric acid consumption in M/sec if after 3.76 minutes there is only 7.68 mole/liter
phosphoric acid present.
I. Given: Ti = 0 sec Ci = 12.24M H3PO4 Tf = 3.76 min = 225.6 sec Cf = 7.68M
II. Required: Rate of consumption of H3PO4
III. Solution: −1 ∆[A] ∆[H3PO4] = Cf – Ci = 7.68M – 12.24M = - 4.56M
Rate A = ------------
a ∆t
∆t = Tf – Ti = 225.6sec – 0sec = 225.6sec
−1 ∆[H3PO4]
Rate H3PO4 = ---------------- −1 (-4.56M) 4.56M
a ∆t Rate H3PO4 = ---------------- = ---------------- = 0.0051M/sec
4 (225.6sec) 902.4sec
CHEMICAL KINETICS
Sn = 119; P = 31; O = 16; H = 1
4H3PO4 + 3Sn(OH)4 → Sn3(PO4)4 + 12 H2O
I. Given: Ti = 0 sec Ci = 0M Sn3(PO4)4 Tf = 2hrs 21 min = 141min Cf = ?

wt. = 43.45g V solution = 654mL = 0.654L
MW Sn3(PO4)4 = (119)(3) + (4)(31) + (16)(16) = 357 + 124 + 256 = 737g/mol
II. Required: Rate of Sn3(PO4)4 formation

III. Solution: 1 ∆[C] Wt 43.45g
Rate C = ------------ M (Cf) = ---------------- = ---------------------------
c ∆t (MW)(V in L) (737g/mol)(0.654 L)
1 ∆[Sn3(PO4)4 ]
Rate Sn3(PO4)4 = -------------------- = 0.0901mole/L or 0.0901M
c ∆t
CHEMICAL KINETICS
Sn = 119; P = 31; O = 16; H = 1
III. Solution:
∆[Sn3(PO4)4] = Cf – Ci = 0.0901M – 0M = 0.0901M
∆t = Tf – Ti = 141min – 0min = 141min
1 ∆[Sn3(PO4)4 ] 0.0901M
Rate Sn3(PO4)4 = -------------------- = --------------------------- = 0.000639M/min
c ∆t 141 min
= 6.39 x 𝟏𝟎−𝟒 M/min
CHEMICAL KINETICS
2. Given the reaction below:
Fe2(SO4)3 + Bi3N5 → FeN + Bi2(SO4)5
a. Bi3N5 was found to be consumed at a rate of – 2.36M/sec. How many hours had
elapsed if only 0.56M Bi3N5 was left from an initial concentration of 3.72M?
b. How many grams of FeN was produced considering the condition in letter a provided
that the total volume is 1.28L? What is the rate of reaction formula and rate of
formation in M/sec of FeN?
c. If the rate of formation of Bi2(SO4)5 is 0.00763M/min, what is its concentration after
365sec? Fe = 56; S = 32; O = 16; Bi = 209; N = 14
CHEMICAL KINETICS
2. Given the reaction below:
5Fe2(SO4)3 + 2Bi3N5 → 10 FeN + 3 Bi2(SO4)5
a. Bi3N5 was found to be consumed at a rate of 2.36M/sec. How many hours had
elapsed if only 0.56M Bi3N5 was left from an initial concentration of 3.72M?
I. Given: R Bi3N5 consumption = -2.36M/sec Cf = 0.56M Ci = 3.72M

II. Required: ∆t in hours
III. Solution:
-1 ∆[Bi3N5] -∆[Bi3N5] - (- 3.16M)
Rate Bi3N5 = -------------------- ∆t = --------------------= -------------------- = 0.6695sec x 1 hr / 3600 sec
b ∆t (R Bi3N5)(b) (2.36M/sec)(2)
= 0.000186 hr
-∆[Bi3N5] = (R Bi3N5)(b)(∆t) ∆[Bi3N5] = Cf – Ci = 0.56M – 3.72M = - 3.16M
-------------- -------------------- = 1.86 x 𝟏𝟎−𝟒 hr
(R Bi3N5)(b) (R Bi3N5)(b)
CHEMICAL KINETICS
formation in M/sec of FeN? Fe = 56; S = 32; O = 16; Bi = 209; N = 14
5 Fe2(SO4)3 + 2 Bi3N5 → 10 FeN + 3 Bi2(SO4)5
I. Given: ∆t = 0.6695 sec V = 1.28L MW Bi3N5 = (3)(209) + (5)(14) = 627 + 70 = 697g/mol
MW FeN = (1)(56) + (1)(14) = 56 + 14 = 70g/mol
II. Required: Wt. FeN in grams, Rate of reaction formula, Rate of formaton FeN in M/sec
III. Solution:
Wt Wt Bi3N5 = (M)(MW)(V in L)
M (Cf) = ----------------
(MW)(V in L) = (0.56 mol/L)(697g/mol)(1.28L)
= 499.6096g Bi3N5
1 coeff. unk.
Wt of unknown = Mass (or weight) given x -------------------- x -------------------- x MW unknown
MW given coeff. given
CHEMICAL KINETICS
5 Fe2(SO4)3 + 2 Bi3N5 → 10 FeN + 3 Bi2(SO4)5
MW FeN = (1)(56) + (1)(14) = 56 + 14 = 70g/mol
= 499.6096g Bi3N5
1 coeff. unk.
Wt of unknown = Mass (or weight) given x -------------------- x -------------------- x MW unknown
MW given coeff. given
1 10mol FeN
= 499.6096g Bi3N5 x -------------------- x -------------------- x 70g/mol
697g/mol 2mol Bi3N5
= 250.88g FeN
CHEMICAL KINETICS
5 Fe2(SO4)3 + 2 Bi3N5 → 10 FeN + 3 Bi2(SO4)5
MW FeN = (1)(56) + (1)(14) = 56 + 14 = 70g/mol
III. Solution:
1 ∆[C] 1 ∆[FeN] 250.88g
Rate C = ------------ Rate FeN = ------------ M (Cf) = ---------------------
c ∆t 10 ∆t (70g/mol)(1.28L)
1 ∆[FeN] ∆[FeN] = Cf – Ci =2.80M FeN

Rate FeN = ------------
c ∆t
∆[FeN] = 2.8M – 0 = 2.80M
CHEMICAL KINETICS
5 Fe2(SO4)3 + 2 Bi3N5 → 10 FeN + 3 Bi2(SO4)5
MW FeN = (1)(56) + (1)(14) = 56 + 14 = 70g/mol
III. Solution:
1 ∆[C] 1 ∆[FeN] 2.80 M
Rate C = ------------ Rate FeN = ------------ = ------------------- = 0.4182M/sec
c ∆t c ∆t (10)(0.6695sec)
1 ∆[FeN]
Rate FeN = ------------
c ∆t
CHEMICAL KINETICS
c. If the rate of formation of Bi2(SO4)5 is 0.00932M/sec, what is its concentration after
63min? Fe = 56; S = 32; O = 16; Bi = 209; N = 14
5 Fe2(SO4)3 + 2 Bi3N5 → 10 FeN + 3 Bi2(SO4)5
I. Given: R Bi2(SO4)5 formation = 0.00932M/sec Ti = 0 min Tf = 63min = 3,780sec
∆t = 3,780sec – 0sec = 3,780sec Ci = 0M
II. Required: Cf or M
III. Solution:
1 ∆[D] ∆[Bi2(SO4)5 ] = (Rate Bi2(SO4)5)(d)(∆t)

Rate D = ------------
d ∆t
= (0.00932M/sec)(3)(3,780sec)
1 ∆[Bi2(SO4)5 ]
Rate Bi2(SO4)5 = --------------------
d ∆t = 105.69M
∆[Bi2(SO4)5 ] = Cf – Ci Cf = ∆[Bi2(SO4)5 ] + Ci = 105.69M + 0M

∆[Bi2(SO4)5 ] = (Rate Bi2(SO4)5)(d)(∆t)
= 105.69M
CHEMICAL KINETICS
Rate Laws and Rate Constants
Each reaction has its own equation that gives its rate as a function of reactant concentrations which is
known as its Rate Law;
To determine the rate law we measure the rate at different starting concentrations;
Rate laws are always determined experimentally;
Reaction order is always defined in terms of reactant (not product) concentrations;
The order of a reactant is not related to the stoichiometric coefficient of the reactant in the balanced
chemical equation.
CHEMICAL KINETICS
In general, rates of reactions increase as concentrations increase since there are more collisions
occurring between reactants;
The overall concentration dependence of reaction rate is given in a rate law or rate expression;
Here’s what a general rate law for a reaction will look like…
Rate = k [𝐴]𝑚 [𝐵]𝑛
- [A] & [B] represent the reactants.
- The exponents m and n are called “reaction orders”.
- The proportionality constant k is called the rate constant.
- The overall reaction order is the sum of the reaction orders: m + n
CHEMICAL KINETICS
A rate law shows the relationship between the reaction rate and the concentrations of
reactants;
– For gas-phase reactants use PA instead of [A].
The rate constant k is a constant that has a specific value for each reaction;
The value of k is determined experimentally, for example:

k is unique for each reaction
k changes with Temperature
CHEMICAL KINETICS
Order of Reaction
A reaction is zero order in a reactant if the change in concentration of that reactant produces no
effect;
A reaction is 1st order if doubling the concentration causes the rate to double;
A reaction is 2nd order if doubling the concentration causes a quadruple increase in rate;
-
3rd order…doubling concentration leads to 23 (or 8 times) the rate.
Note-- The rate constant, k, does not depend on concentration!
Once we have determined the rate law and the rate constant, we can use them to
calculate initial reaction rates under any set of initial concentrations.
CHEMICAL KINETICS
1. A series of experiments is performed for the system
2A + 3B + C → D + 2E
2nd order 1st order zero order
When the initial concentration of A is doubled, the rate increases by a factor of 4.

When the initial concentration of B is doubled, the rate is doubled.
When the initial concentration of C is doubled, there is no effect on rate.
a) What is the order of reaction with respect to each of the reactants?

Overall order = 2 + 1 + 0 = 3rd order
b) Write an expression for the rate equation. Rate = k [𝐴]𝑚 [𝐵]𝑛
Rate = k [𝑨]𝟐 [𝑩]𝟏 [𝑪]𝟎 Rate = k [𝑨]𝟐 [𝑩]
CHEMICAL KINETICS
2. Given the equation: 3CO2 + Ni2O3 → Ni2(CO3)3
1st order 2nd order
Several experiments were performed to determine the order of reaction and the rate constant
for this reaction. The following were observed:
Experiment Initial [CO2], M Initial [Ni2O3], M Observed Initial

Number Rate, M/s
1
2
1.2
2.4
0.6
0.6
3.85 x 10−3
7.70 x 10−3
} doubled
3 0.6 1.2 2.89 x 10−3

4 0.6 2.4 1.16 x 10−2
} quadrupled
a. Write rate law / expression and determine the overall order of reaction. = 0.016 / 0.00289
=4
b. What is rate constant in experiment number 3 in the table?
CHEMICAL KINETICS
2. Given the equation: 3CO2 + Ni2O3 → Ni2(CO3)3
1st order 2nd order
Several experiments were performed to determine the order of reaction and the rate constant
for this reaction. The following were observed:
a. Write rate law / expression and determine the overall order of reaction.
Overall order = 1 + 2 = 3rd order Rate = k[CO2]^1[Ni2O3]^2
b. What is rate constant in experiment number 3 in the table?

I. Given: [CO2] = 0.6M [Ni2O3] = 1.2M Rate = 2.89 x 10−3 𝑀/𝑠
II. Required: k
Rate 2.89 x 10−3 𝑀/𝑠 2.89 x 10−3 𝑀/𝑠
III. Solution: Rate = k [𝐴]𝑚 [𝐵]𝑛 k = -------------------- = -------------------- = --------------------
[CO2]1 [Ni2O3]2 1
[0.6𝑀] [1.2𝑀] 2
0.864𝑀3𝑀2
Rate = k [CO2]1 [Ni2O3]2
------------ ---------------------- = 0.0033/ 𝑀2 s
[CO2]1 [Ni2O3]2 [CO2]1 [Ni2O3]2
CHEMICAL KINETICS
3. Reactant A reacts with reactant B to produce product C. It was determined via different
experimental trials that the reaction is first order with respect to reactant A and also first order
with respect to reactant B. Write the rate law / expression for this reaction and determine the
initial concentration of reactant B if the reaction has a rate law constant of 5.49/Ms and a rate
of 5.5M/min. Reactant A was found to have an initial concentration of 7.85M.
I. Given: A = 1st order B = 1st order k = 5.49/Ms
rate = 5.5M/min x 1min / 60sec = 0.0917M/sec [A] = 7.85M
II. Required: rate law / expression and Ci
III. Solution: A + B → C
Rate = k [𝐴]𝑚 [𝐵]𝑛 Rate = k 𝐴 [𝐵] Rate 0.0917M/sec

------------ ------------ [B] = --------------- = ---------------
k𝐴 k𝐴 𝑘[𝐴] (5.49/Ms)[7.85𝑀]
Rate = k [𝐴]1 [𝐵]1
= 0.0021M
CHEMICAL KINETICS
4. Use the following data to determine a) the reaction order of A and B, b) the rate constant (k),
and c) the rate law equation for the reaction that proceeds by the equation 2A + B → C.
Experiment [A] [B] Rate (M/s)
1 0.25 0.10 0.012
Quadrupled
2 0.25 0.20 0.048 B = 2nd order
3 0.50 0.10 0.024 Doubled
A = 1st order
I. Given: A = 1st order B = 2nd order rate = 0.024M/sec [A] = 0.50M [B] = 0.10M
II. Required: k
Rate 0.024M/s 0.024M/s
III. Solution: Rate = k [𝐴]𝑚 [𝐵]𝑛 k = -------------------- = -------------------- = --------------------
[A]1 [B]2 [0.50𝑀]1 [0.10𝑀]2 0.05𝑀3 𝑀2
Rate = k [𝐴]1 [𝐵]2
= 0.48/ 𝑀2 s
CHEMICAL KINETICS
Change of Concentration with Time / Integrated Rate Law
For zero order reaction:
[A]t = -kt + [A]0
where [A]t = concentration of [A] after some time, t
k= reaction rate constant in units of M/s
t= time in seconds
[A]0 = initial concentration of A
For 1st order reaction:

ln[A]t = -kt + ln[A]0
CHEMICAL KINETICS
Change of Concentration with Time / Integrated rate Law
For 2nd order reaction:
1 / [A]t = kt + 1 / [A]0
CHEMICAL KINETICS
Half-Life
Half-life is the time taken for the concentration of a reactant to drop to half its original
value.
For zero order reaction:
t½ = [A]0 / 2k - Unit of k = M/s
For first order reaction:
t½ = 0.693 / k - Unit of k = /s (per second)
For 2nd order reaction:
t½ = 1/ k[A]0 - Unit of k = /Ms (per Molar second)
CHEMICAL KINETICS
1. What is the half-life for the decomposition of NOCl when the concentration of NOCl is 0.15
M? The rate constant for this second-order reaction is 8.0 × 10−8 L/mol/s.
2. The half-life of a reaction of compound A to give compounds D and E is 8.50 min when the
initial concentration of A is 0.150 mol/L. How long will it take for the concentration to drop
to 0.0300 mol/L if the reaction is (a) first order with respect to A or (b) second order with
respect to A?
3. The anticancer drug cisplatin hydrolyzes in water with a rate constant of 1.5 × 10−3 /min at
pH 7.0 and 25°C. Calculate the half-life for the hydrolysis reaction under these conditions. If
a freshly prepared solution of cisplatin has a concentration of 0.053 M, what will be the
concentration of cisplatin after 5 half-lives? after 10 half-lives? What is the percent
completion of the reaction after 5 half-lives? after 10 half-lives?
CHEMICAL KINETICS
1. What is the half-life for the decomposition of NaOCl when the concentration of NaOCl is
0.15 M? The rate constant for this second-order reaction is 8.0 × 10−8 L/mol/s.
I. Given: [NaOCl] = = 0.15M k = 8.0 × 10−8 L/mol/s or 8.0 × 10−8 /Ms

II. Required: t1/2 NaOCl
III. Solution:
t½ = 1/ k[A]0
1 1
t½ = -------------------- = ------------------------------------ = 8.33 × 𝟏𝟎𝟕 s
k[A]0 (8.0 × 10−8 /Ms)[0.15M]
CHEMICAL KINETICS
initial concentration of A is 0.150 mol/L. How long will it take for the concentration to drop to
0.0300 mol/L if the reaction is (a) first order with respect to A or (b) second order with respect
to A?
I. Given: t1/2 = 8.50min [A]0 = 0.15M [A]t = 0.0300M
II. Required: t @ first order and t @ 2nd order
III. Solution:
First Order Second Order ln[A]t - ln[A]0 = -kt 1 / [A]t – 1 / [A]0 = kt
------------ ------------ --------------------- ------------
-k -k k k
t½ = 0.693 / k t½ = 1/ k[A]0
ln[A]t = -kt + ln[A]0 ln[A]t - ln[A]0 1/[A]t – 1/[A]0
1 / [A]t = kt + 1 / [A]0 t = -------------------- t = --------------------
-k k
First Order Second Order

CHEMICAL KINETICS
to A?
III. Solution: First Order Second Order
ln[A]t - ln[A]0 1/[A]t – 1/[A]0
t = -------------------- t = --------------------
-k k
(k)(t½) = 0.693 (k) [A]0(t½) = 1
------------ ------------ ------------ ------------
t½ = 0.693 / k t½ t½ t½ = 1/ k[A]0
[A]0(t½) [A]0(t½)
0.693 0.693 1 1
t½ = -------------------- k= ------------ t½ = -------------------- k= ------------
k t½ k[A]0 [A]0(t½)
CHEMICAL KINETICS
to A?
III. Solution: First Order Second Order
0.693 0.693 1 1
k= ------------ = ------------ k= ------------ = ----------------------
t½ 8.50min [A]0(t½) (0.15M)(8.50min)
= 0.0815/min = 0.7843/M min

CHEMICAL KINETICS
to A?
III. Solution: First Order k = 0.0815/min
ln[A]t - ln[A]0
t = --------------------
-k
ln[0.0300] - ln[0.15] -3.5066 – (-1.8971) -1.6095
= --------------------------- = --------------------------- = --------------------------- = 19.75min
-0.0815/min -0.0815/min -0.0815/min
CHEMICAL KINETICS
to A?
III. Solution: Second Order k = 0.7843/M min
1/[A]t – 1/[A]0
t = --------------------
k
1/[0.03M] – 1/[0.15M] 33.33/M – 6.67/M 26.66/M

= ---------------------------- = ---------------------------- = ---------------------------- = 33.99min
0.7843M/min 0.7843M/min 0.7843M/min
CHEMICAL KINETICS
pH 7.0 and 25°C. Calculate the half-life for the hydrolysis reaction under these conditions. If a
freshly prepared solution of cisplatin has a concentration of 0.053 M, what will be the
concentration of cisplatin after 5 half-lives? after 10 half-lives? What is the percent completion
of the reaction after 5 half-lives? after 10 half-lives?
I. Given: k = 1.5 × 10−3 /min pH = 7.0 T = 25°C [A]0 = 0.053M
II. Required: t1/2, [cisplatin] after 5 and 10 half-lives and %completion after 5 and 10 half-lives
III. Solution:
The reaction is first order

CHEMICAL KINETICS
III. Solution:
ln[A]t - ln[A]0 0.693 0.693

t = -------------------- t½ = -------------------- = -------------------- = 462min
-k k 1.5 × 10−3 /min
0.693 @ 5 half-lives, t = 462min x 5 = 2,310min

t½ = --------------------
k @ 10 half-lives, t = 462min x 10 = 4,620min
CHEMICAL KINETICS
III. Solution:
ln[A]t - ln[A]0 -kt + ln[A]0 -3.465 + (-2.9375)

t = -------------------- [A]t = e [A]t = e
-k -6.4025
@ 5 half-lives, t = 462min x 5 = 2,310min [A]t = e
ln[A]t - ln[A]0 = -kt (- 1.5 × 10−3)(2,310) + ln[0.053] [A]t = 0.0017M = 1.66 × 𝟏𝟎−𝟑 𝐌
[A]t = e
ln[A]t = -kt + ln[A]0 [cisplatin] after 5 half-lives
CHEMICAL KINETICS
III. Solution:
ln[A]t - ln[A]0 -kt + ln[A]0 -6.93 + (-2.9375)

t = -------------------- [A]t = e [A]t = e
-k -9.8675
@ 10 half-lives, t = 462min x 5 = 4,620min [A]t = e
ln[A]t - ln[A]0 = -kt (- 1.5 × 10−3)(4,620) + ln[0.053] [A]t = 0.000052M = 5.18 × 𝟏𝟎−𝟓 𝐌
[A]t = e
ln[A]t = -kt + ln[A]0 [cisplatin] after 10 half-lives
CHEMICAL KINETICS
III. Solution:
[A]0 - [A]t 0.053 – 0.0017
% completion = -------------------- x 100 = -------------------- x 100 = 96.79%
[A]0 0.053
[A]t = 0.0017M
[cisplatin] after 5 half-lives
CHEMICAL KINETICS
III. Solution:
[A]0 - [A]t 0.053 – 0.000052
% completion = -------------------- x 100 = -------------------- x 100 = 99.90%
[A]0 0.053
[A]t = 0.000052M
[cisplatin] after 10 half-lives
CHEMICAL KINETICS
Reaction Mechanisms
reaction mechanism – process by which a reaction occurs
Elementary Steps
elementary steps – each step in a reaction
molecularity – defines how many molecule are consumed
unimolecular – if only one molecule involved in step
bimolecular – elementary step involving collision of two reactant molecules
termolecular – elementary step involving simultaneous collision of three
molecules
elementary steps in multi-step mechanism must always add to give chemical equation of
overall process
intermediate – product formed in one step and consumed in a later step
CHEMICAL KINETICS
Reaction Mechanisms
Rate Laws of Elementary Steps
If reaction is known to be an elementary step then the rate law is known
rate of unimolecular step is first order (Rate = k[A])
rate of bimolecular steps is second order (Rate = k[A][B])
first order in [A] and [B]
if double [A] than number of collisions of A and B will double
CHEMICAL KINETICS
Reaction Mechanisms
Rate Laws of Multi-step Mechanisms

rate-determining step – slowest elementary step
determines rate law of overall reaction
Mechanisms with an Initial First Step

intermediates usually unstable, low and unknown concentrations
whenever a fast step precedes a slow one, solve for concentration of
intermediate by assuming that equilibrium is established in fast step
CHEMICAL KINETICS
Catalysis
catalyst – substance that changes speed of chemical reaction without undergoing a
permanent chemical change
Homogeneous Catalysis
homogeneous catalyst – catalyst that is present in same phase as reacting
molecule
catalysts alter Ea (activation energy) or A
generally catalysts lowers overall Ea for chemical reaction
catalysts provides a different mechanism for reaction
CHEMICAL KINETICS
Catalysis
Heterogeneous Catalysis
exists in different phase from reactants
initial step in heterogeneous catalyst is adsorption
adsorption – binding of molecules to surface
adsorption occurs because ions/atoms at surface of solid extremely reactive
Enzymes
biological catalysts
large protein molecules with molecular weights 10,000 – 1 million amu
catalase – enzyme in blood and liver that decomposes hydrogen peroxide into water and oxygen
substrates – substances that undergo reaction at the active site
lock-and-key model – substrate molecules bind specifically to the active site
enzyme-substrate complex – combination of enzyme and substrate

BSMLS I - MT Chemical Kinetics 1

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BSMLS I - MT Chemical Kinetics 1

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CHEMICAL KINETICS

Antonio G. Celajes Jr., RCh

Introduction to Analytical Chemistry

a. Qualitative versus Quantitative Chemistry

Solutions, Colloids, Acids and Bases

a. Types of Solution and Colloids

b. Factors that affect solubility

c. Electrolytes and Non-electrolytes

e. Determination of concentrations of solution

f. The Colligative properties of solution

a. Computations based on balanced equations

For the reaction A → B there are two ways of measuring rate:

Δ[A] = change in concentration of A over time period Δt

Changes in concentrations of the reactants and/or products is inversely proportional to their

In general, for the reaction: aA + bB → cC + dD

−1 ∆[A] −1 ∆[B] 1 ∆[C] 1 ∆[D]

4H3PO4 + 3Sn(OH)4 → Sn3(PO4)4 + 12 H2O

I. Given: Ti = 0 sec Ci = 0M Sn3(PO4)4 Tf = 2hrs 21 min = 141min Cf = ?

II. Required: Rate of Sn3(PO4)4 formation

I. Given: R Bi3N5 consumption = -2.36M/sec Cf = 0.56M Ci = 3.72M

1 ∆[FeN] ∆[FeN] = Cf – Ci =2.80M FeN

1 ∆[D] ∆[Bi2(SO4)5 ] = (Rate Bi2(SO4)5)(d)(∆t)

∆[Bi2(SO4)5 ] = Cf – Ci Cf = ∆[Bi2(SO4)5 ] + Ci = 105.69M + 0M

Rate laws are always determined experimentally;

Reaction order is always defined in terms of reactant (not product) concentrations;

The value of k is determined experimentally, for example:

When the initial concentration of A is doubled, the rate increases by a factor of 4.

a) What is the order of reaction with respect to each of the reactants?

Experiment Initial [CO2], M Initial [Ni2O3], M Observed Initial

3 0.6 1.2 2.89 x 10−3

b. What is rate constant in experiment number 3 in the table?

Rate = k [𝐴]𝑚 [𝐵]𝑛 Rate = k 𝐴 [𝐵] Rate 0.0917M/sec

For 1st order reaction:

I. Given: [NaOCl] = = 0.15M k = 8.0 × 10−8 L/mol/s or 8.0 × 10−8 /Ms

First Order Second Order

= 0.0815/min = 0.7843/M min

1/[0.03M] – 1/[0.15M] 33.33/M – 6.67/M 26.66/M

The reaction is first order

ln[A]t - ln[A]0 0.693 0.693

0.693 @ 5 half-lives, t = 462min x 5 = 2,310min

ln[A]t - ln[A]0 -kt + ln[A]0 -3.465 + (-2.9375)

ln[A]t - ln[A]0 -kt + ln[A]0 -6.93 + (-2.9375)

Rate Laws of Multi-step Mechanisms

Mechanisms with an Initial First Step

exists in different phase from reactants

initial step in heterogeneous catalyst is adsorption

adsorption – binding of molecules to surface

adsorption occurs because ions/atoms at surface of solid extremely reactive

large protein molecules with molecular weights 10,000 – 1 million amu

substrates – substances that undergo reaction at the active site

lock-and-key model – substrate molecules bind specifically to the active site

enzyme-substrate complex – combination of enzyme and substrate

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