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Unit 1: Kinetics and Equilibrium

ANSWER KEY Chem 1B

Name

Kinetics
1.
1.

2.

3.

4.

2.

What factors affect rates? Give examples of each.


Nature of the reactants- physical state, surface area-Examples Li, Na, K react with
water at different rates, liquid gasoline burns slower that gas vapor, powders react
faster than larger chunks, dry solid reactants generally react slower than solutions of
the same reactants.
The concentration/pressures of the reactants -Examples many times a reaction rate
slows as the concentration of the reactants decrease. At any time an instantaneous rate
can be calculated from the negative slope of the tangent to the curve of time (x axis)
verses reactant concentration (y axis) or the positive tangent to the time verses product
concentration.
The temperature at which the reaction occurs -ExamplesThe rate increases as the
temperature increases since more colliding particles will have the minimum energy to
react.
The presence of a catalyst, enzymes -ExamplesCatalyst alter the
mechanism/pathway of the reaction. The activation energy is lowered and the steps in
the reaction vary from that without a catalyst.
Express the general rate of reaction in terms of the rate of change of each
reactant and each product in the following reaction (this is an instantaneous rate
used for relatively short time periods):
2 C2H6 (g) + 7 O2 (g) 4 CO2 (g) + 6 H2O (l)
Rate = -[ C2H6]/2t = -[ O2]/7t= [ CO2]/4t= [ H2O]/6t

Write the balance equation and rate law expression for the combination reaction
of NO (g) and O2 (g) to produce NO2 (g) if the reaction is second order in NO,
first order in O2 and 3rd order overall.
Rate = k[NO]2[O2]

2 NO (g) + O2 (g) 2 NO2 (g)


4

Rate data were collected for the following reaction at a particular temperature:
A + 2B C + 2D
Experiment

Initial [A]

Initial [B]

0.20 M

0.10 M

Initial Rate
form. C
4.0 x 10 -4
M/min

a)
b)
c)
d)

0.20 M

0.30 M

0.60 M

0.30 M

0.40 M

0.20 M

1.2 x 10 -3
M/min
3.6 x 10 -3
M/min
?

What is the order of the reaction with respect to A, B, and overall?


[A] = 1; [B] = 1; overall = 2
What is the rate law expression?
Rate = k[A] [B]
What is the value of k?
k = 0.020 M-1min-1
Calculate the rate for experiment 4. Rate = 1.6 x 10-3 M/min

Consider a graph where x is time in seconds and y is the concentration of


reactant A in Molarity, [A]. The graph shows a straight line whose y intercept is
0.400 M and the slope is -0.0350 M/sec for the reaction: A Products
a)
What is the order of the reaction?
Zero
b)
Write the rate law expression.
Rate =k
c)
Determine the rate constant, k, for this reaction. k = 0.0350 M/sec

The reaction 2A products is second order in A and has the form Rate = k[A] 2
where k has the value 6.0 x 10-4 M-1 min-1. The reaction is at an initial
concentration of 0.100 M and 318K.
a)
How long is the first half-life?
t1/2 = 1.7 x 104 min; 280 hr
b)
How much time is required for the concentration to reach 0.085 M?
2.9 x 103 min

According to collision theory, to have an effective collision reactants must be in


the proper ORIENTATION towards each other at the time of collision and
have THE MINIMUM ENERGY REQUIRED, Ea to rearrange outer electrons in
breaking bonds and forming new ones.

The following is a proposed mechanism:


1)
A + B <==> AB
(fast, equilibrium)
2)
AB + A A2B
(slow)
3)
A2B + B A2 + B2
(fast)
a)
What is the overall equation for this mechanism? 2 A + 2B A2 + B2
b)
What is the rate law expression for the mechanism? Rate =k[A]2[B]
c)
What happens to the initial rate of formation of AB (step 1) if the
concentrations of A and B are both doubled? Rate =k[2A][2B] 2 x 2 = 4
the rate is 4 times greater
c)
What happens to the rate of the reaction if the concentrations of A and B
are both doubled?
Rate =k[2A]2[2B] 22 x 2 = 8, the rate is 8 times greater
d)
Which letter(s) represents a reaction intermediate? AB, A2B

The activation energy for a given reaction is 95 kJ/mol. If the rate constant is
0.042 sec-1 at 30C, what is the value of the rate constant at 50C?
ln (k1/k2) = (Ea/R)(T2-1 T1-1);

10

k = 0.43 s-1

How does a catalyst affect The activation energy?


equilibrium constant?

The rate?

The

The activation energy: Generally a catalyst lowers the activation energy


The rate: A catalyst will speed up the rate
The equilibrium constant: A catalyst has no effect on the equilibrium constant
11

The rate and therefore the specific rate constant of a particular reaction doubles
when the temperature is increased from 25C to 40C. Calculate the activation
energy, Ea, for this reaction.
ln (k1/k2) = (Ea/R)(T2-1 T1-1);

12

Ea = 35.8 kJ/mol

With regard to collision theory, (k = Zfp),


a)
What do each of the symbols, (k, Z, f, p) represent?
Z = collision frequency, how often particles collide. This is directly
proportional to the root mean squared speed, rms. From the kinetic molecular
theory we learned rms = square root of 3RT/Molecular weight. As the
temperature increases we know that the molecules move faster and will collide
a bit more frequently. But, by doing the math one can find a 10C rise has less
than a 2% increase in collision frequency. Z does not noticeably affect the
specific rate constant as the temperature changes. This is certainly far off from
the tripling affect we saw in the NO and Cl2 example.
p =

fraction of collisions with proper orientation (independent of Temp).

f = fraction of collisions with the activation energy required for success.


This energy allows the particles to create an activated complex at the height of
the energy profile. This factor is greatly affected by small temperature changes.
f = e-Ea/RT
Using the same NO and Cl2 example, f = e-Ea/RT and given that the
activation energy is 85 kJ/mol, one can solve for f. At 25C, f = 1.3 x 10-15
and at 35C, f = 3.9 x 10-15 which accounts for our k being over 3 times larger.
b)

What factor is most responsible for the fact that the rate of a chemical
reaction generally increases sharply with a rise in temperature?
f = fraction of collisions with the activation energy required for success.

13

Propose a plausible 3-step mechanism that fits with the information given.
+2
Overall reaction 2 Ce+4 + Tl+1 Mn 2 Ce+3 + Tl+3
Rate = k[Ce+4][Mn+2]
Step 1 is the rate determining slow step.
Mn+3 is a reaction intermediate produced in step 1 and used up in step 2
Mn+4 is a reaction intermediate produced in step 2 and used up in step 3
Tl+1 is not used until step 3
Step 1)
Ce+4 + Mn+2 Mn+3 + Ce+3
Slow
+4
+3
+4
+3
Step 2)
Ce + Mn Mn + Ce
Fast
+1
+4
+2
+3
Step 3)
Tl + Mn Mn + Tl
Fast

14

The experimentally observed rate law for the reaction: H2 + 2 ICl 2 HCl + I2
(all are gas) is Rate = k[ICl][H2].
a) (Circle) the following mechanism(s) that is (are) plausible? (can be more than
one)
b) For all the mechanisms identify, Reactants, Products, (Reaction
Intermediates), and Catalysts
c) Identify the molecular of each step in all the mechanisms (uni-, bi-, termolecular).
Molecularity
Mechanism 1
Step 1
H2 + 2 ICl 2 HCl + I2
Slow
Mechanism 2
Step 1
2{ ICl I + Cl }
Fast
Step 2
I + Cl + H2 HCl + HI
Slow
Step 3
HI + I + Cl HCl + I2
Fast
Mechanism 3
Step 1
2ICl Cl2 + I2
Slow
Step 2
Cl2 + H2 2 HCl
Fast
Mechanism 4
Step 1
H2 + ICl HCl + HI
Slow
Step 2
ICl + HI HCl + I2
Fast
Mechanism 1
(Mechanism 2)

Mechanism 3
(Mechanism 4)

Step 1
Step 1
Step 2
Step 3
Step 1
Step 2
Step 1
Step 2

H2 + 2 ICl 2 HCl + I2
Slow
2{ ICl I + Cl }
Fast Equilibrium
I + Cl + H2 HCl + HI
Slow
HI + I + Cl HCl + I2
Fast
2ICl Cl2 + I2
Slow
Cl2 + H2 2 HCl
Fast
H2 + ICl HCl + HI
Slow
ICl + HI
HCl + I2
Fast

Ter
Uni
Ter
Ter
Bi
Bi
Bi
Bi

15

Explain why a mixture of natural gas and air formed by leakage of gas from a
pipe can stand for a long time without reacting but explodes if a spark is
introduced.
The reaction requires a spark in order to provide the needed activation energy to
initiate the reaction.

16

Describe the characteristics of the specific rate constant, k. Include if and how k
and its units are affected by temperature, time, concentration, overall order,
catalyst, etc.
Information on k, the specific rate constant
1. Its value is for a specific reaction represented by a balance equation
2. Its value will change if a catalyst is added
3. Its for a specific temperature and will change when Temp changes
4. Its units depend on the overall order. 1/(M(overall order 1 time)
5. It does not alter with the concentration changes
6. It does not change with time
7. It is determined through experiments

17

a)
The table shows concentration changes with time as a reaction A
products
takes place. Fill in the table.
ln[A]
1/[A]
time (hour)
[A] (Molarity)
-1.61
5.00 M-1
0
0.200 M
-2.30
10.0 M-1
1
0.100 M
-3.00
20.0 M-1
3
0.050 M
-3.22
25.0 M-1
4
0.040 M
-3.69
40.0 M-1
7
0.025 M
b)
c)
d)
e)
f)
g)

What order is the reaction? Zero First Second


Second
Plot a graph labeling the axes appropriately for the determined order,
which will give a straight line. 1/[A] vs hours
Calculate the value of the specific rate constant, k.
k = 5.00 M-1hr-1
How long will it take [A] to reduce to 0.085 M?
1.35 hr
How long is the first half-life of this reaction?
1.00 hr
How long is the third half-life of this reaction?
4.00 hr

Equilibrium
18

Do most reactions go to completion (all reactants forming all products until one
reactant is used up)? No

19

a)

b)

c)
d)

e)
20

Write the equilibrium constant (Kc or Kp) for the following reaction:
2SO2 (g) + O2 (g) 2 SO3 (g)
H = -198.4 kJ/mol rxn
2
2
Kc = [SO3] /[SO2] [O2] or
Kp = [PSO3]2/[PSO2]2[PO2]
Does K remain constant as...
1)
temperature varies? No, K changes
If temperature increases how will the equilibrium shift? How
does K change? As Temp increases this reaction will shift in the
endothermic direction, for this example it is reversed.
2)
initial concentrations vary? Yes, K is constant
If you start with only products instead of reactants how does
K change? There is no effect on K
3)
reaction coefficients vary? No, K is changes
If the equation is written as SO2 + 1/2 O2 SO3, how doe
K change? One must take the effect and add it as a power to the
value of K. For the example above the reaction is cut in half so the
value of K is square rooted.
if K << 1 then are products or reactants favored? REACTANTS
How are Kc and Kp different? By what equation are they related?
Kp represents all activities came from partial pressures and Kc represents all the
activity values came from molarities.
Kp = Kc(RT)n
What is the difference between Q and K? Q is for any concentrations, while
K must be for equilibrium conditions.

What is Le Chateliers Principle? Explain the meaning of STRESS added to a


system at equilibrium and how the system reacts.
(FROM THE NOTES) Le Chateliers Principle and How to Manipulate the Reaction:
If a system at equilibrium is disturbed by a change in temperature, pressure, or the
concentration of one of the components, the system will shift its equilibrium position as to
counteract the effect of the disturbance.
Changes to Consider:
a)
Concentration of any substance: Adding a reactant or removing a product will
shift the reaction forward. Removing a reactant or adding a product will shift in
reverse.
b)
Volume / Partial Pressures of any gas substance: Increasing the volume will
decrease the partial pressures and the reaction will shift to create more pressure,

c)

d)

the direction that has more moles of gas. No effect occurs when an inert gas is
added that does not participate in the reaction.
Temperature: Increasing the temperature will favor the endothermic reaction to
shift reduce the extra energy added. Decreasing the temperature will in the
direction of the exothermic reaction.
Catalyst: This has no affect on a system at equilibrium; it will just allow a
system to reach the equilibrium quicker.

21

For the reaction Br2 (g) + F2 (g) 2 BrF (g)


Kc = 54.7
a) What are the equilibrium concentrations of all the gases if the initial
concentrations of bromine and fluorine were both 0.100-M with no BrF?
x =0.079 M; 0.021 M Br2, 0.021 M F2 and 0.158 M BrF
b) What are the equilibrium concentrations if the initial concentrations of all
three gases (Br2, F2, & BrF) start at 0.100 M?
x = 0.068 M; 0.032 M Br2, 0.032 M F2 and 0.236 M BrF

22

The system below is at equilibrium and has the following concentrations in a 1.00
L flask: [H2O2] and [CO] both are 0.37 M while [H2O] = [CO2] = 0.74 M. If
0.75 moles of ONLY hydrogen peroxide are added, calculate the new equilibrium
concentrations.
H2O2 (g) + CO(g) H2O (g) + CO2 (g)
Kc = 4.0, calculated from initial equilibrium values
This needs the quadratic equation to solve.
x = 0.16M; 0.96 M H2O2, 0.21M CO, 0.90 M H2O, 0.90M CO2

23

For the reaction at a 25C temperature: N2O4 (g) 2 NO2 (g)


If Kc = 250, what is Kp? Kp = 6120

24

What is the equilibrium constant (Kc , Kp , Keq) expression for ...


a)

MgCO3 (s) MgO (s) + CO2 (g)


Kc = [CO2],

b)

Keq = Kp = [PCO2]

2HCl (aq) + Mg (s) H2 (g) + MgCl2 (aq)


Keq = [PH2][MgCl2]/[HCl]2,

Kc = [H2][MgCl2]/[HCl]2

Kp = not possible,
c)

Fe+3 (aq) + SCN-1 (aq) FeSCN+2 (aq)


Kc = Keq = [FeSCN+2]/[Fe+3] [SCN-1]
Kp = not possible,

25

What is the value of Keq when G = -150 kJ/mol at 25C? G = -RTlnKeq


Use R = 8.314 J/mol K

26

(this belongs in Unit II)

Keq = 2 x 1026

In the Haber process NH3 is manufactured from N2 and H2. At 25C, Kp = 3.6 x
108. To increase the rate of reaction the reaction is run at a higher temperature.
Use the van't Hoff equation to calculate Kp at 450C
N2 (g) + 3 H2 (g) 2NH2 (g)
H = -92.2 kJ
Van't Hoff eq. ln(K2/K1) = H/R (1/T1 - 1/T2)
Use R = 8.314 J/mol K (this belongs in Unit II) Kp = 0.11

REVIEW
27

What volume of 18.0 M H2SO4 is required to prepare 1.50 L of 2.00 M H2SO4?


0.167 L

28

What is the difference between an equivalence point and an end point?


Equivalence point is the stoichiometric amounts, End point is a visible sign to stop the
titration.

29

What is the M of KOH if you have 38.7 ml of KOH solution, and 43.2 ml of 0.223
M HCl is required to react with all the KOH in a titration reaction?
0.249 M

30

What does it mean to be a strong electrolyte? Which types of substances will be


strong electrolytes? What are the strong acids? What are the strong soluble
bases?
Strong electrolytes dissociate almost completely into ions.
Strong electrolytes can be Strong Acids, Strong Bases and Soluble Salts.
Strong Acids: HCl, HBr, HI, HNO3, HClO4, HClO3, H2SO4
Strong soluble Bases: Metal Hydroxides in groups 1A (excluding HOH) and IIA
(excluding the first two; Be, Mg)

31

For the following double displacement reactions, predict the products and
balance the reactions, include terms (s), (l), (g), & (aq):
Use NR for no
reaction.
a) KNO3 (aq) +

(NH4)3PO4 (aq) No Reaction-all spectators

b) HCl (aq)

+ K2SO3 (aq)

2HCl (aq)

+ K2SO3 (aq)

2KCl (aq) + H2O (l) + SO2 (g)

c) NaCl(aq) + AgNO3(aq)
NaCl(aq) + AgNO3(aq) NaNO3 (aq) + AgCl (s)
Acids and Bases
32

Give a definition for an acid and a base for each of the 3 theories; Arrhenius,
Bronsted-Lowry, and Lewis.
Arrhenius theory
Acid has H+ its willing to give up in aqueous solution
Base has OH- its willing to give up in aqueous solution
Bronsted-Lowry theory
Acid is a proton donor
Base is a proton acceptor
Lewis theory
Acid will accept an electron pair
Base will donate an electron pair

33

What is the acid, base, conjugate base and acid in the equation below?
NH3 + H2O NH4+ + OHBase---------------------conj. acid
acid-----------------------conj. base

34

a)

What are some properties of an acid? a base?


Properties of acids:
Tastes sour, reacts with metals to liberate hydrogen, reacts with
carbonates to liberate CO2, neutralizes bases, neutralizes metal
oxides, change color of indicators, conduct electricity, react with a salt
containing a conjugate base of a weaker acid
Properties of bases:
Tastes bitter, slimy to touch, neutralizes acids, conducts electricity,
changes color of indicators.

b)

List the strong acids and strong bases.


Strong Acids:
HCl, HBr, HI, HClO4, H2SO4, HNO3, HClO3
Strong Bases:
LiOH, NaOH, KOH, RbOH, CsOH, FrOH, Ca(OH)2, Sr(OH)2,
Ba(OH)2, Ra(OH)2

c) Describe the relationship between the strength of a strong acid and its
conjugate base.
Strong acids will always want to react to form weaker acids and vice versa.
As an acid increases in strength its conjugate base decreases in strength.

35

d)

What is the relationship between the bond strength of a binary acid and
the acid strength? As the bond strength increases the acid strength decreases
since it takes more effort to break the bond and put the H+ into solution.

e)

What is the relationship between the oxidation state of an oxyacid with the
same central atom and the acid strength?
As the oxidation state increase so does the acid strength. As an example in
H2SO4, S has an oxidation state of +6 and it is a stronger acid than H2SO3 in
which sulfur has a +4 oxidation state.

f)

What other factors affect acid strength? (carboxylic acids, small highly
charged metal ions)
As more electronegative elements are attached to a carboxylic acid, the stronger
the acid. The smaller a metal size and as the positive charge increases, the
stronger the acid.

When would a soluble salt be basic? neutral? acidic? or unsure without knowing
Kb or Ka values?
Write the molecular equation, complete ionic equation, and net ionic equation for
the following salts, indicate whether each salt is: basic, acidic, neutral, or unsure.
NaCl, NH4NO3, KF, CH3NH3NO2
A salt that hydrolyzes to make a strong acid and a strong base is neutral an example is
NaCl + H2O <==> NaOH + HCl
Na+1 + Cl-1 + H2O <==> Na+1 + OH- + H++ Cl-1
H2O <==> OH- + H+
A salt that hydrolyzes to make a strong acid and a weak base is acidic an example is
NH4NO3 <==> NH3 + HNO3
NH4+1 + NO3-1 <==> NH3 + H++ NO3-1
NH4+1 <==> NH3 + H+
A salt that hydrolyzes to make a weak acid and a strong base is basic an example is
KF + H2O <==> KOH + HF
K+1 + F- + H2O <==> K+1 + OH- + HF
F- + H2O <==> OH- + HF

A salt that hydrolyzes to make a weak acid and a weak base is uncertain in acidity or
basicity unless more information such as Kb and Ka values are known
CH3NH3NO2 + H2O CH3NH2
+ HNO2
-4
Kb = 4.4 x 10
Ka = 4.5 x 10-4
CH3NH3+1 + NO2-1 + H2O CH3NH2 + HNO2
This salt is neutral since the Ka is approximately equal to Kb.
36

What is the concentration of hydroxide ions in 0.25M Ba(OH)2? 0.50 M [OH-1]

37

Water will autoionize, what does that mean? Kw is the equilibrium constant for
water Kw = [H+][OH-] = 1 x 10-14 = KaKb at 25C. pH+pOH = 14. What is the
pH range for acid? neutral? and base solutions?
Autoionize means that an ionic substance will spontaneously ionize until it
reaches its equilibrium.
pH < 7 in acidic solution ; pH = 7 in neutral solution; pH > 7 in basic solution

38

For 0.020 M HCl calculate [H+], pH, pOH, [OH-]


-13
[H+] = 0.020 M; pH = 1.70 ; pOH = 12.30 ; [OH-] = 5.0 x 10 M

39

For cyanic acid write the ionization equation. What is the [HCN], [CN-], [H+],
pH, % ionization in a 0.040 M HCN solution. Ka of HCN = 4.9 x 10-10
-6
[HCN] = 0.040 M ; [CN-] = 4.4 x 10 M ;
-6
[H+] = 4.4x 10 M ; pH = 5.35 ; % ionized = 0.011%

40

Given that the pH of a NH3 solution is 10.95. Calculate the molarity of NH3 in
-5
-2
this solution. Kb = 1.8 x 10
[NH3] = 4.5 x 10 M

41

Calculate the concentrations of [H+], [OH-], [H2S], [HS-], and [S-2] in 1.00 M
H2S solution.
Ka1 of H2S = 9.5 x 10-8,
Ka2 of HS- = 1 x 10-19
-4
-11
[H+] = 3.1 x 10 M ; [OH-] = 3.2 x 10 M ; [H2S] = 1.00 M ;
-4
-2
-19
[HS-] = 3.1 x 10 M ; [S ] = 1 x 10 M

42

What is the hydrolysis constant, Kb of CN- if Ka of HCN = 4.9 x 10-10.


Calculate the [OH-], pOH, pH and % hydrolysis of CN- in a solution that
contains 0.22 M KCN.
-1
-5
-3
Kb for CN = 2.0 x 10 ; [OH-1] = 2.1 x 10 M; pOH = 2.67; pH = 11.33;
% hydrolysis = 0.95 %

43

Look up the appropriate Ka and Kb constants.


neutral, or basic?
Basic

Would NH4CN be acidic,