Name
Kinetics
1.
1.
2.
3.
4.
2.
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]
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
?
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
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
The rate?
The
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
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)
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.
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
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
24
b)
Keq = Kp = [PCO2]
Kc = [H2][MgCl2]/[HCl]2
Kp = not possible,
c)
25
26
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
28
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
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) +
b) HCl (aq)
+ K2SO3 (aq)
2HCl (aq)
+ K2SO3 (aq)
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)
b)
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
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
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
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