C O D E - 43867 - C H E M 104CD Spring 2012 Exam I - Paper Exam

Name: 7 pt Consider the following reaction performed at 273 K : 2 N O (g) + CL, (g) Experiment 1 [NO](M) 0.00100 2 NOC1 (g)
2

[C1 ](M) 0.00100

Rate of tion(M/s) 1.4

reac-

0.00100

0.00200

2.8

0.00200

0.00200

2.8

What is the rate law for this reaction? 1. A O rate=k[NO][Cl ]

2

C^LiaieskJCy? / fc)^n^Ie^kfCla^-3
:

7 pt The reaction:

A - B

+ C

MS
is known to be second order with respect to A and to have a rate constant of 0 . 2 4 3 M / s at 2 8 9 K . A n experiment was run at this temperature where [A] = 0 . 4 1 7 M . Calculate the concentration of B after 0.151 seconds has elapsed.

2.

A Q 0.00478

Q 0.00628

C Q 0.00704

D Q 0.380

E Q 0.402

7 pt The rate of the reaction between hemoglobin (Hb) and carbon monoxide (CO) was studied at 229 K and the rate law was determined to be rate = k[Hb][CO]. When the [Hb] = 0.00871 M and [CO] = 0.00317 M the initial rate of the reaction was found to be 0.2697 M / s . What would the initial rate of the reaction be for an experiment at 229 K where [Hb] = 0.0373 M and [ C 0 ] = 0.0225 M ?
c o

C .ooJtfflt

-00*17]

|^ -

2697

(in K/s) 3. A Q 7.26

C Q 9.26 D Q 10.5 E Q H-8

C O D E - 43867 - C H E M 104CD Spring 2012 Exam I - Paper Exam

7 pt Consider the following information for the reaction A products, where [A] = 1.17 M .
D

Reaction rxn 1 rxn 2 rxn 3 rxn 4 rxn 5

E 75.0 100. 100. ,50.0 75.0

(kJ/mol) | 7<T '

A E (kJ/mol) 50.0 -75.0 25.0 25.0 -50.0

t the reactions will have the fastest initial rate of reaction? 4. / A O rxn 5 B O rxn 3 C O rxn 1 D O rxn 4 E Q rxn 2 ft

Q 5 o

I n

7pt
2

Balance the following unbalanced redox reaction (assume acidic solution if necessary):

M n + + CLj -> M n 0 " + C l "

4

Indicate the coefficient that w i l l be used for each species in the overall balanced equation. >Mn +
2

5.

A O

1
4

B O

C O

D O

E O

It

> Mn0 " 6. A Q 1 >Cl2 7. A Q 1

B O B O

2 2

C O C Q

3 3

D O D Q

4 4

E O E Q

5 5

7 pt Consider the following statements based on collision theory. Indicate if the statement is true or false.

t> A catalyst works by lowering the activation energy of a reaction, allowing a greater number of collisions to overcome the actiyation barrier. 8. [jLQ True B O False > For a given reaction, collisions of any energy can lead to the formation of a product. 9. A O True B O False > Increasing the concentration of the reactants i n a first order reaction will increase the number of successful collisions that take place i n the reaction. f - jr\ ^ ^ % 10. A O True B O False ^
L

> Collisions with the appropriate orientation will always lead to product formation. 11- A O True B O False > Increasing the temperature of a reaction increases the energy i n the random collisions which will lead to a larger percentage of collisions yielding products. 12. A Q True B Q False

C O D E - 4 3 8 6 7 - C H E M 104CD Spring 2012 Exam I - Paper Exam

7 pt For the following two problems use the given half reactions to "construct" a galvanic cell.

2 +

2 e- - M g

cell

=i2.37 V V

C u + + 2 e- - C u
2

&> =0M
n

Predict the standard potential of the galvanic cell at 298 K . (in V j 13. A Q 1-45
B Q

1-69

C Q

1-98

D Q

2.32 / " E Q 2.71

7pt Predict which species will be found in the following portion of the galvanic cell. > Aapde-Btectrode Vf-AQjUg^ B O Cu C O Mg²⁺ D O Cu²⁺ > Cathode solution 15. A O Mg B O Cu C O Mg²⁺ Cu²⁺ > Cathode electrode, 16. A O Mg ^ ^ C ^ C O Mg²⁺ D O Cu²⁺
/

E O Pt

E O Pt

E O Pt

> Anode 17. A O //SQ D Q

solution Mg B O Cu Mg²⁺ Cu²⁺

E Q Pt

C O D E - 43867 - C H E M 104CD Spring 2012 Exam I - Paper Exam

7 pt Consider a galvanic cell that is set up under standard conditions and allowed to react. Evaluate if the following statements are true or false.

> Electrons will flow from the cathode half cell to the anode half cell.
18. A O True B O False

6 > The half reaction with the lower standard reduction potential will be found i n the cathode portion of the cell.
19. A O True B O False

i -fz

> Electrons are produced spontaneously at the anode electrode.

20. A O True B O False

'

^'

> The mass of the anode electrode will increase as the galvanic cell approaches being "dead".
21. A O True B O False

t> The salt bridge acts as a second pathway for electrons to flow, thereby "completing" the electrical circuit.
22. A Q True B Q False

7 pt la your lab you are studying the kinetics of the degradation of a pain killer i n the human liver. You are monitoring the concentration of the pain killer over a period of time. The initial concentration of the pain kilter i n your experiment was 1.69 M . After 9.437 hours the concentration was found to be 0.8450 M . In another 18.87 hours the concentration was found to be 0.4225 M (t = 28.307 hours overall). If another experiment were set up where the initial concentration of the pain killer was 0.281 M , how long would it take for the pain killer concentration to reach 0.0213 M ? (in hours)

C O D E - 43867 - C H E M 104CD Spring 2012 Exam I - Paper Exam

7 pt Consider the following data for the decomposition of nitrous oxide ( N 0 ) to N and 0
2 2

gas at 315 K :

2 t/.o
Experiment 1 2 3 Mechanism 1 [N 0] 0.337 0.674 2.359
2

0.

(M)

Initial Rate ( M / m i n ) 0.00296 0.0119 0.145

N 0 ^ N + O. N 0 + O ^ N + 0
2 2 2 2

y/"
2

fast equihbrium slow fast equilibrium slow fast equilibrium slow slow ^

Mechanism 2

2 N 0 ^ N 0 2 N + 0 N 0
2 4 2 4 2 2

Mechanism 3

2N O^N 0 1/2 N 0 N
2 4 2 4 2

+ O
2

Mechanism 4

N 0 + N 0
2 2

2N + 0 +
2

ts o
z

O + O ^ 0 > Mechanism 4
24. A O Plausible B O Not valid

fast equilibrium

V *
7

ftJ

> Mechanism 3
25. A O Plausible B O Not valid

> Mechanism 2
26. A O Plausible B O Not valid

t> Mechanism 1
27. A Q Plausible B Q Not valid

7 pt Consider the cell described below at 293 K :

ell
2

Sn | Sn + (0.989 M ) | | P b + (0.963 M ) | P b
2

-I . II3

Given E 2 + _ = -0.131 V , E 2 + _ = -0.143 V . Calculate the cell potential after the reaction has operated long enough for the Sn + to have changed by 0.381 m o l / L . (in V)
0 P B P B S N ( S N

28. A Q

0.00101

B Q

0.00111

D Q

0.00129

E Q

0.00133

it

0li

C O D E - 43867 - C H E M 104CD Spring 2012 Exam I - Paper Exam

7 pt A n experiment you are performing i n your lab requires you to generate fluorine gas through an electrolytic hydrolysis set up. The current experiment you wish to perform requires that you supply 7.57 moles of F gas per hour from your set up. W h a t is the minimum amperage current your electrolysis apparatus w i l l need?
2

2HjO + 2e--H + 20HE = -0.83 V F + 2e--2FE = 2.87 V

2 2

2+1,0

+ _ ^

Hi

2off'

(ink)
29. A Q 208 B Q 260. C Q 325 D Q 406 E Q 507

: (|j

7 pt A concentration cell is built based on the following half reactions by using two pieces of zinc as electrodes, two Zn solutions, 0.143 M and 0.425 M , and all other materials needed for a galvanic cell. W h a t will the potential of this cell be when the cathode concentration of Z n has changed by 0.045 M at 299 K ?
2 + 2 +

Z n + + 2 e2

Zn

E = -0.761 V

(in V)
30. A Q -0-752 B Q -0.00907 /Q Q.QMOj/ D Q 0.0181 E Q 0.0202

C O D E - 43867 - C H E M 104CD Spring 2012 Exam I - Paper Exam

7pt ' Consider the cell described below at 295 K :

Fe | Fe +(1.35 M ) | | Cd +(2.05 M) | C d
2 2

<e>j Given E 2 + - _ = -0.403 V and be when the cell is dead? (ihH)

C D

2 e

C d

F E

2+

-_

F e

= -0.441 V . W h a t will the concentration of the C d EO 1-89

2 +

solution

3 5 . AO 0.145

BO 0.148

/pO

0.163^>O 0.239

7 pt Consider the f o l l o w i n g W f r e a c t i o n s at 298 K

dd^^^d ^

"f f c

Fe + + 2 e- - Fe E = --0441 V C d + -I- 2 e- C d E = -0.403 V

2 2

' ~ - ( F J + -f- Z C *
z

' Cc/

A galvanice cell based on these half reactions is set up under standard conditions where each solution is 1.00 L and each electrode weighs exactly 100.0 g. How much will the C d electrode weigh when the nonstandard potential of the cell is 0.02749 V ? ^ ^ . 017 W - ,03 2 - T /
M

36. A Q 5 8 . 9

B Q 118

C Q 144/

D Q 174

E Q 190.

7 In your lab you are s t b d y m g a certain biochemical bacterial metabolic pathway (shown below). Y o u have initial data that suggests that if you could inhibit this pathway you would have the "next pemcillinj . but first you need to determine the activation energy for the rate determining step of this process. ^-" ,
1

enzyme + substrate * product 1 + product 2 It is known that under the conditions you are performing your experiment the rate law for the reaction is: rate = k[enzyme] [substrate] .
2

You set up an experiment at 311 K where [enzyme] = 0.00387 M and [substrate] = 1.51 M . A plot of ln[enzyrne] versus time (seconds) gives a straight line relationship with a slope of -0.007331. Previous studies have shown that a plot of ln(k) at a series of different temperatures gives a y-intercept of 0.48674. What is the activation energy for this reaction? (in k J j 37. A O 5.28 B O 7.66 CO H I l D O / l
r

E O 23.3

too

$~2-l5*-0*

C O D E - 43867 - C H E M 104CD Spring 2012 Exam I - Paper Exam

7pt

Consider the fictional reaction:

A + B -. F + G which is catalyzed by reagent C.

The rate of this reaction was monitored by looking at the disappearance of B under several different experimental setups at 298 K . Experiment [A](M) [B](M) [C](M) R a t e of d i s appearance of B(M/s) 4.75e-05

0.300

0.0500

0.0500

0.300

0.100

0.0500

4.75e-05

0.300

0.0500

0.100

9.51e-05

4 5

0.400 0.400

0.0500 0.0500

0.200 0.0500

0.000254 6.34e-05

Step 1: A + C - D Step 2: D -+ E + C Step 3: E + B ^ F + G

Given the previous information, which of the following situations would lead to a plausible reaction mechanism?

> Step 2 as the rate determining step. Step 1 is a fast equihbrium step while step 3 is a fast step. 38. A O Plausible Mechanism B O Not a valid mechanism t > Step 2 as the rate determining step. A l l other steps fast steps. 39. A O Plausible Mechanism B O Not a valid mechanism > Step 3 as the rate determining step. A l l other steps fast steps. 40. A O Plausible Mechanism B O Not a valid mechanism > Step 3 as the rate determining step. Step 2 is a fast equihbrium step while step 1 is a fast step. 41. A Q Plausible Mechanism B O Not a valid mechanism > Step 1 as the rate determining step. A l l other steps fast steps. 42. A Q Plausible Mechanism B Q Not a valid mechanism

7pt Consider a cell based on the following line notation and half reactions:

Cd|Cd +||Fe +|Fe

2 2

1'

where

2+

= -0.403

and

F E

2+

-_

F e

= -0.441.

Evaluate whether the following statements are true or false. D > Electrons spontaneously flow from anode to cathode
43. A O True B O False

t> The half reaction with the higher standard reduction potential will be the anode portion of the cell
44. A O True B O False

t > Oxidation takes place at the anode 45. A Q True B Q False 7 pt In class we watched a demonstration where the color of the solution oscillated between orange and blue. This is a very comphcated reaction with multiple pathways the reaction can take. One pathway can be described as follows:

H 0
2

+ 3 I- + 2 H + -> I - + 2 H 0
3 2

Step Step Step Step Step

1. 2. 3. 4. 5.

Hs%+ tfy'-> H 0 + H 0 + -t*fr - ^ 0 + H O I HOI OH- + I O H - + ft* -+/*yt> Ia - if

3 2 3 2 2

How many of the following statements are correct based on the information given?

> There are no catalysts i n this reaction 46. A O Correct B O Incorrect > If step 2 is the rate determining step, and step 1 is a fast equilibrium step, this reaction would be third order overall
47. A O Correct B O Incorrect

> The reaction is first order with respect to H 0

2

48. A O Correct

B O Incorrect

> A n energy diagram of this reaction would have 5 peaks and the starting materials would be higher i n energy than the products
49. A Q Correct
Printed from

B Q Incorrect
Licensed under G N U General P u b l i c License

LON-CAPAMSU

Useful Information Hour Exam II A G = A G + R T in(Q)

0

R = 8.314 J/mol K - 0.0821 L atm/mol K

A G = -nFE AG = -nFE

Ecell * Ecell (cathode) - Ecell (anode) RT

F = 96485 C/mol e"

k = Ae

+ w =

ln(A)

In

_ lis

ri

r
J

K = C + 273 Order

-Pext(Vf-Vi) Integrated Rate Law

L a tin

101. 3

Differential Rate law rate = k

Half-life

[A] = -kt + [A]

t

2k 1 ln[A]t = -kt + l n [ A ]
0

rate = k| A |

In 2

14

PI

rate = k l A f

17.1

Standard Reduction Potentials at 26'C (298 K) for Many Cornwion Half-Reactions Half-Reaction % (V) 2.87 1.99 1.82 1.78 1.70 1.69 1.68 1.60 1.51 1.50 1.46 1.36 1.33 1.23 1.21 1.20 1.09 1.00 0.99 0.96 0.954 0.91 0.80 0.80 0.77 0.68 0.56 0.54 0.52 Half-Reaction 4QH C u * + 2e - Cu HgjCfj 4- 2e - 2Hg + 2CV AgCl + e"' -# Ag + i t S O / + 4iV + 2c - 4 H3SO, + HjO Q f * + - _ Cu* 2H' + 2e H; l V + 3e" - Fe
2 e v t

^ r t + c" - * Ag* Co " + r - * C o " 2H,0 HA 2H" + 2c' 0>* 4-. e" Ce * PbSO, + 2I%0 pbOj + H* + S O / + 2c" HA' + J * " - * MrO* + 2HjO p- + 2 H 4- I0 - - - l O f * H 0 MnCV + * M * * 5c -*> M r . " + 4HjO A H " * 3e~ Au ftOj + 411* * 2e~ - * Pb** 2H/J
3

Oj * 2" -acr
+

CrvO,* + I4H + fa" -+ 2Cr'* + 7HjO Oj + 4H* + 4c' - i 2H 0 MnO, + 4H* + 2e" - * M B * * + 2Hj.o 10,- + 6H + 3" * | i , + 3HjO Btj + 2e" -+ 2Br" VOj* + 2 H 4 t -+ VO** + HjO ABQ4" + 3e" - * AM + 4CT 1*V + - 4 H + i* ~ N O 2HjO
2 + 4 4

a a +e ciOj fflg * + 2e" -~* Hgi * Ag* + " - * Ag Hfc * + 2e* - * 2Hg rV* f e~ - * Fe* 0, + 2ir + 2e" ~* H A IfaO. + e" -+ Mn0 ~ lj + 2c > 21" C* + e -> Cu
5 2 5 + 2 4

pt* * + | r - * Pb S n ' + 2e" -> Sn Ni** + 2e" Ni PbS0 + 2c" - Pb + S O / " Cd *' + 2c" * Cd F e + 2e" -> Pe Q * + e" > Cr" Cr * + 3e- - * Or Zn*' + 2c' /n 2H,0 + 2o" - Hj + 2 0 H " Kfa * + 2e~ -* Mn A l * + 3e" * A ! Hj + 2e" - * 2 H Mfe * + 2e" - * Mg L a ' * + 3e~ - * U Na + e" - Na Ca ~ + 2e' - Ca B a + 2e" - * Ba K* + e K L i * + e~ - * U
2 1 4 2 ,+ 3 3 2 3 + 2 + 2 J+

0.40 0.34. 0.27 0.22 0.20 0.16 0.00 -0.036 -0.13 -0.14 -0.23 -0.35 -0.40 -0.44 -0.50 -0.73 -0.76 -0.83 -1.18 -1.66 -2.23 -2.37 -2.37 -2.71 -2.76 -2.90 -2.92 -3.05