UP Academic League of Chemical Engineering Students (UP ALCHEMES)

Academic Affairs Committee - Reviews and Tutorials Series, A.Y. 2015-2016

Chem 17 LE 1 (SOLUTIONS)

I. Modified True or False.

1. If a gas undergoes pressure-volume work in a container fitted with a piston, P in w=-PV refers to the
pressure of the gas inside the container.
FALSE- outside
P refers to the external pressure because the force against the piston comes from the external
pressure

2. The standard entropy of formation of hydrogen gas is zero.

FALSE- hydrogen ion
Standard entropies of formation are not zero, but that of the hydrogen ion is defined as zero to set a
standard for the other ions

3. The entropy of glass at absolute zero is zero.

FALSE- non zero
Glass is amorphous. The third law holds for perfectly crystalline substances

4. The combustion of 1 mole of ethane (C2H6) leads to a greater increase in entropy than the combustion of
1 mole of ethanol (C2H5OH).
FALSE- lesser increase in entropy
The balanced equations are:

7
C2 H6 + O 2CO2 + 3H2 O
2 2
C2 H5 OH + 3O2 2CO2 + 3H2 O

The change in moles of gas for the combustion of ethane is while that of ethanol is 1, thus the
combustion of ethanol leads to greater entropy.

5. The reaction involving HClO2 and NaOH is more endothermic than that of HOCl and NaOH.
FALSE - more exothermic
HClO2 is a stronger acid than HClO, thus less energy is needed to abstract the proton so more of the
energy can be released as heat.

6. If G>0, then the reaction is spontaneous.

FALSE - Suniv

7. In an Ellingham Diagram, the y-intercept and slope of a line are the H and S of the reaction,
respectively.
FALSE - H and -S
The equation G=H-TS can be rearranged as G=(-S)T+H. When compared against y=mx+b,
the slope and y-intercept are -S and H respectively.

8. The rate of a reaction always depends on the concentration of the reactants.

FALSE- sometimes
Zero order reactions do not depend on concentrations

9. In the graph of energy versus progress of reaction, the number of maxima equal to the number of
intermediates involved in the reaction.
FALSE- transition states
 The maxima occur when two reactants collide to form the transition state. The intermediates occur
at the minima of the reaction profile.

10. The half-life of a reaction always depends on the initial concentration.

FALSE- sometimes
The half-life of a first order reaction does not depend on initial concentration.

II. Multiple Choice

Directions: Write the capital letter of the choice corresponding to the best answer

1. What is the final temperature when 4.0 g of iron at 150 C is immersed in 306 mL of octane (C8H18) at 25
C. (cFe = 0.450 J/gK; cC8H18 = 2.15 J/gK; C8H18 = 0.703 g/mL)
A. 25.6 C C. 25.2 C
B. 25.4 C D. 24.4 C

2. The calorimetry experiment was carried out with 3.00 mL 1.00 M NaOH and 2.00 mL 1.00 M HCl and Ccal
was determined to be 21.81 J/K. Calculate the new Ccal if 4.00 mL 1.00 M BaCl2 and 2.00 mL 1.00 M
Na2CO3 are to be used. Assume all aqueous solutions have the same heat capacity and density as water.
The specific heat of BaCO3 is 0.4325 J/gK.
A. 21.98 J/K C. 26.34 J/K
B. 26.16 J/K D. 26.51 J/K

In the calibration step, 5.00 mL of liquid was present. In the experiment, there is an extra 1.00 mL of
solution and 0.002 mol or 0.39462 g of BaCO3 precipitate. The extra heat capacity is therefore

(1.00 )(1.00 )(4.184 ) + (0.39462 )(0.4325 ) = 4.35 .

Adding this to the original heat capacity yields 26.16 J/K

3. A cylindrical container with radius 15.0 cm is fitted with a movable piston which is pushed down 5.00
cm by a constant pressure of 1.50 atm. The system simultaneously releases 1.47 cal of heat. What is U
for the system?
A. -543 J C. 531 J
B. -531 J D. 543 J

For a cylindrical container, V=Ah. Substituting this into w=-PV yields w=-PAh. The sign of w
should be positive since work is done on a piston which is true because h<0 (note final minus initial).
The sign of q is negative since heat is released from the system.

4. In which among the following reactions is U closest to H?

A. C2 H4 (g) + H2 (g) C2 H6 (g)
B. () + () ()
C. 2N2 O(g) N2 O4 (g)
D. S2 O3 2 (aq) + 2H + (aq) S(s) + H2 O(l) + SO2 (g)

The difference between H and U is a PV term, therefore the reaction with the least change in
moles of gas has a U closes to H.

5. Calculate U for the reaction N2 H4 (l) + O2 (g) N2 (g) + 2H2 O(g) in an isobaric container held at 298
K. The reaction is Hrxn=-534 kJ/mol
A. -536 kJ/mol C. -1.94103 kJ/mol
B. -532 kJ/mol D. -3.01103 kJ/mol

Use H = U + RTngas
6. Estimate the bond energy of a C-H bond if the enthalpy of combustion of ethane (C2H6) is -1560.7 kJ/mol.
bond energies: BE(C-C) = 348 kJ/mol; BE(O=O) = 495 kJ/mol; BE(C=O) = 799 kJ/mol; BE(O-H) = 463
kJ/mol.
A. 389 kJ/mol C. 909 kJ/mol
B. 519 kJ/mol D. 1818 kJ/mol

7. Calculate the entropy of reaction for the following reaction: 4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g)
Substance S/(J/Kmol)
NH3(g) 192.3
O2(g) 205.0
NO(g) 210.7
H2O(g) 188.7
A. 180.8 J/K C. 2230.8 J/K
B. 412.1 J/K D. 2083.6 J/K

8. What is the boiling point of carbon tetrachloride gas given the following values: Hliquid = -135.4 kJ/mol,
Hgas = -102.9 kJ/mol, Sliquid = 216.4 J/(mol K), Sgas = 309.9 J/(mol K)?
A. 273.50 C C. 74.44 C
B. 347.59 C D. 0.347 C

Use G = H - TS and set G to zero because boiling is a process in equilibrium.

9. Which of the following statements is incorrect?

A. Hvap for Br2 is the same as Hf[Br2(g)]
B. Svap for Br2 is the same as S[Br2(g)]
C. Gvap for Br2 is the same as Gf[Br2(g)]
D. None of the above.

Standard entropies of formation are nonzero at 25 C even for elements at their most stable form.

10. Ammonium nitrate is a solid substance that explodes exothermically and produces a lot of gas. Which
line in an Ellingham diagram best represents the explosive decomposition of ammonium nitrate?

D. The explosion produces a lot of gas, therefore its S should be large. Since the slope of an Ellingham
diagram is -S, the correct answer is D since it has the most negative sloping line.

11. In the reaction H2 S + SO2 S + H2 O, hydrogen sulfide is consumed at a rate of 0.572 mol/s. At
what rate is sulfur produced?
A. 0.572 mol/s
B. 0.858 mol/s
C. 1.14 mol/s
D. Cannot be determined; rate law is needed
 The balanced equation is 2H2 S + SO2 3 S + 2H2 O. Use the rate expression to calculate the rate of
formation of sulfur.
1 d[H2 S] 1 d[S]
=
2 dt 3 dt

12. The reaction time between tert-butyl chloride (tBuCl) and NaI was recorded with varying
concentrations. Determine the rate law and the rate constant of the reaction.
Trial [tBuCl]0/M [I-]0/M rate/(M/s)
1 3.42 2.45 0.214
2 3.42 4.90 0.214
3 6.84 4.90 0.428

A. rate=k[tBuCl]; k=0.0626 s-1

B. rate=k[tBuCl]; k=0.0626 M-1s-1
C. rate=k[tBuCl][I-]; k= 0.0128 M-1s-1
D. rate=k[tBuCl][I-]; k= 0.0255 M-1s-1

Doubling the amount of tBuCl doubles the reaction rate, therefore the reaction is first order in tBuCl.
Doubling the amount of I- does not affect the reaction rate, therefore the reaction is first order in I-

13. The dimerization reaction of acetic acid in a nonpolar solvent is a second order reaction. If the initial
concentration of acetic acid is 0.837 M and the half-life of the reaction is 12.8 s, find the concentration
of acetic acid after 82.9 s.
A. 1.87 M C. 0.112 M
B. 0.256 M D. 9.4010-3 M

Use the integrated rate law for second order reactions. The half life and rate constant of a second order
1
reaction are related by t 1 =
2 k[A]0

14. Determine the order and the rate constant of the following reaction:
t/s [A]/M
0.217 0.796
0.342 0.709
0.696 0.540
0.723 0.531

A. zero order; k=0.512 Ms-1

B. first order; k=0.793 s-1
C. second order; k=0.986 M-1s-1
D. second order; k=1.24 M-1s-1

Using linear regression, a plot of t against 1/[A] produces the straightest line. The slope of this line is
equal to k

15. What temperature increase from 25.0C is required to double the reaction rate of a reaction with an
activation energy of 58.6 kJ/mol?
A. 8.49 C C. 10.5 C
B. 9.01 C D. 25.1 C

1
Use the two-point form of the Arrhenius equation ln (1 ) = (
2
) 1. Since the rate is doubled and
2 1
the concentrations of the reactants are the same, then k1=2k2
16. The activation energy of a reaction is 53.7 kJ/mol and that of the reverse reaction is 34.9 kJ/mol. What
is Grxn?
A. 18.8 kJ/mol C. 88.6 kJ/mol
B. -18.8 kJ/mol D. -88.6 kJ/mol

A drawing of the reaction profile shows that the energy of the product side is 18.8 kJ/mol higher than
that of the reactants.

17. Which statement regarding the proposed reaction mechanism below is true?
A2 + B AB + A
AB + C AC + B
A2 + C AC + A

A. B is an intermediate, C is a catalyst
B. AB is an intermediate, B is a catalyst
C. AC is a catalyst, A2 is an intermediate
D. AB is a catalyst, B is an intermediate

B is consumed in the first step and is regenerated in the second step; therefore, it is a catalyst.
Likewise, AB is produced in the first step and consumed in the second, thus it is an intermediate.

18. Determine the rate constant and the order of the following reaction.
[A]0/M t1/2/s
0.747 0.774
0.342 1.69
0.219 2.64
0.107 5.41
A. zero; k=6.01 Ms -1

B. zero; k=0.0831 Ms-1

C. second; k=0.579 M-1s-1
D. second; k=1.72 M-1s-1

The half life increases as initial concentration decreases which is characteristic of a second order
1
reaction (note t 1 = ). A plot of 1/[A]0 and t1/2 yields a straight line with slope 1/k.
2 k[A]0
19. Curve O represents the energy diagram of a reaction. Which will most likely be the resulting curve if a
catalyst is added to the reaction?

B. A catalyst reduces the activation energy of a reaction by providing alternative paths. If the original
reaction occurs in a single step, the catalyzed reaction should occur in more than one step, thus making
A wrong and B correct.

20. The diagram below shows a plot of energy vs extent of reaction for two competing reactions A + B
AB and A + C AC. Suppose that a beaker containing A also contains excess and equimolar amounts of
B and C. Which of the following will increase the amount of AB formed?
 A. Increase the temperature of the beaker
B. Leave the beaker in a relatively cool temperature
C. Use a catalyst that lowers the activation energy of AC A + C
D. Use an inhibitor that increases the activation energy of AB A + B

Increasing the temperature allows the products and reactants to jump across energy barriers. The
reactants and products will cycle back and forth until most of the reactants end up producing the most
thermodynamically stable product AC and not AB.

Catalysts and inhibitors lower the activation energy of both the forward and reverse reaction, thus
options C and D will end up producing more AC and not AB.

III. Problem Solving.

Directions: Do what is asked. Observe proper rules on significant figures for questions involving calculations.

1. Liquefied petroleum gas is a mixture primarily composed of propane (C3H8) and butane (C4H10). It is
used in households for cooking and heating purposes. The enthalpies of combustion of propane and
butane are -2202.0 kJ/mol and -2877.5 kJ/mol respectively.
a. Calculate U (in kJ/mol) for the combustion of one mole of propane and for one mole of butane
at 25 C.

Derive an expression relating the entalphy and internal energy changes of combustion.
= +
= + ()
= + ()
= +
=

=

=
Um and Hm refer to the molar internal energy and molar enthalpy respectively v refers to the
stoichiometric coefficients

The balanced equations are:

3 8 + 52 = 32 + 42 0 = 1
13 3
4 10 + 2 2 = 42 + 52 0 = 2
Um[C3H8]= -2204.5 kJ/mol
Um[C4H10]= -2881.2 kJ/mol

b. An 18.52 g sample of liquefied petroleum gas is burned in a bomb calorimeter and the reaction
released 921.5 kJ of heat. Assuming that the sample is composed of propane and butane only,
calculate the mole fraction of propane in the mixture.
 Set up the systems of equations for the moles of propane and butane. Use U since the reaction
occurs at a constant volume.
Let n3 and n4 be the moles of propane and butane respectively.
Let M3 and M4 be the molar mass of propane and butane respectively.
Let q be the heat released by the reaction (-921.5 kJ).
Let m be the mass of the sample
[3 8 ] 3 + [4 10 ] 4 =
3 3 + 4 4 =

Solve for the moles of propane and butane

n3=0.1828 mol
n4=0.1800 mol

Calculate the mole fraction of propane

3
3 =
3 + 4
x3=0.5039

2. A Styrofoam ball calorimeter was used to determine the enthalpy of the following redox reaction in basic
medium:

Ba(s) + CrO4 2 (aq) Ba2+ (aq) + Cr(s)

For the calibration of the calorimeter, 24.0 mL of 0.500 M NaOH was mixed with 16.0 mL of 0.800 M
HNO3. The temperature of the calorimeter rose from 25.0 C to 27.5 C. After calibration, a lump of
barium metal weighing 0.4000 g with 98% purity was dropped into a solution containing 39.0 mL of
0.025 M of Na2CrO4 and 1.0 mL of 0.500 M NaOH to make the solution basic. The reaction was allowed to
finish by swirling the mixture and letting the precipitation to complete. The temperature of the
calorimeter rose from 25.0 C to 30.07 C.
a. Determine the heat capacity of the calorimeter, in J/C.

Determine the limiting reactant

1 2
(24.0 )(0.500 ) ( ) = 12.0 2
1
1 2
(16.0 )(0.800 + ) ( ) = 12.8 2
1 +

Limiting reactant: nLR=0.012 mol OH-

=
=

=

Ccal=268.08 J/K

b. Determine the enthalpy of the redox reaction, in kJ/mol. (MBa = 137.3 g/mol; MCr = 52.00 g/mol;
cBa = 28.1 J/molK; cCr = 23.4 J/molK)

Balanced Reaction: 42 + 3 + 4 2 32+ + + 8

Determine the limiting reactant

1 1
(0.4000 )(0.98) ( )( ) = 0.952
137.3 3
1
(39.0 )(0.025 4 2 ) ( ) = 0.975
1 4 2
 Limiting reactant: 2.855110-3 mol Ba
Solids formed: 9.516910-4 mol Cr

Make corrections to Ccal

, = +
Ccal,corr = 268.1023 J/K

=
=
,
=

Hrxn=-476.0879 kJ/mol (for 1 mol Ba)

Hrxn=-1.43103 kJ/mol (for 3 mol Ba or 1 mol rxn)

c. Determine the standard enthalpy of formation of chromate. (Hf[Ba2+(aq)] = -537.6 kJ/mol;

Hf[H2O(l)] = -285.8 kJ/mol; Hf[OH-(aq)] = -230.0 kJ/mol)

Set up the equation for Hrxn using Hf of the products and reactants. Solve for Hf[CrO42-(aq)]
= (3 [Ba2+ (aq) ] + [Cr(s) ] + 8 [ () ])
(4 [2 () ] + 3 [Ba(s) ] + [CrO4 2 (aq) ])
= (3 [Ba2+ (aq) ] + 8 [ () ]) (4 [2 () ] + [CrO4 2 (aq) ])
[CrO4 2 (aq) ] = 3 [Ba2+ (aq) ] + 8 [ () ] 4 [2 () ] =
H[CrO42-]=-881 kJ/mol

3. The table below shows the Grxn of the oxidation of a certain metal with one mole of oxygen gas at
various temperatures.
T/K Grxn/(kJ/mol)
1137 -817
1446 -789
1844 -714

a. Find H and S of the reaction using linear regression.

Use linear regression with x=-T and y=G to fit the line G=S(-T)+H

H=-991 kJ/mol
S=147 J/molK

b. Identify the metal using the given Ellingham Diagram.

H is the y-intercept of the graph and the Tl line has the y-intercept closest to -991 kJ/mol,
therefore the metal is thallium.
 c. At what temperature can the oxide of this metal be reduced by carbon?

Find the temperature at which the 2 + 2 2 line intersects with the 2 + 2 2

line

T=2000 C

d. What metals can reduce the oxide of this metal at 1400 K?

Convert Kelvin to degrees Celsius since the graph uses the latter for temperature. At 1673K, the
lines for Al, Mg, and Ca are below Tl, thus these metals can reduce TlO.

4. The reaction mechanism for the reaction of acetic acid (HOAc) and ethyl chloride(EtCl) in basic media is
shown as follows:

HOAc + OH OAc + H2 O (fast)

OAc + EtCl EtOAc + Cl (slow)
HOAc + OH + EtCl EtOAc + Cl + H2 O (total)

a. Using the steady state approximation, derive the rate law for the overall reaction. Let k1 be the
rate constant for the forward direction of the fast reaction, k-1 for the reverse direction of the fast
reaction and k2 for the slow reaction.

The rate is determined by the slowest step, therefore

= 2 [ ][]

In the steady state approximation, the concentration of the intermediate (OAc-) is assumed to be
constant, which means it is being produced and consumed at equal rates
() = ()
1 [HOAc][OH ] = 1 [ ][H2 O] + 2 [ ][]
1 [HOAc][OH ] = [ ](1 [H2 O] + 2 [])
1 [HOAc][OH ]
[ ] =
(1 [H2 O] + 2 [])
 Substituting [OAc-] in the rate law,
1 [HOAc][OH ][]
= 2
(1 [H2 O] + 2 [])

b. A small amount of acetic acid and a large excess of all other substances appearing in the rate law
is used for an experiment. If the initial concentration of acetic acid is 0.00538 M and the
concentration becomes 0.00137 M in 28.3 s, find the apparent rate constant for this reaction.

Since the concentrations of all other reactants are large, they can be assumed to be constant for
the duration of the reaction; thus, the rate law reduces to a pseudo-first order reaction.
= [HOAc]

The apparent rate constant can then be calculated using the integrated rate law for first order
reactions
[HOAc]
=
[HOAc]0
1 [HOAc]
=
[HOAc]0
k'=0.0483 s-1

5. An experiment is performed to determine the orders of reaction of methyl iodide (CH3I) and hydroxide
ion (OH-) in the following reaction:

CH3 I + OH CH3 OH + I

In the first experiment, the concentration of CH3I was monitored in a 10.0 M NaOH solution at three
different temperatures.
T=0.00 C T=25.0 C T=???
t/s [CH3I]/M t/s [CH3I]/M t/s [CH3I]/M
5 0.282 5 0.0173 5 0.0895
10 0.159 10 5.9710-4 10 0.0160
15 0.0894 15 2.0610-5 15 2.8610-3

In the second experiment, a solution that is 5.00 M CH3I and 0.100 M OH- is prepared and the osmotic
pressure of the solution was observed. The reaction vessel contains a solid surface that adsorbs CH3OH,
thus removing it from solution.
t/s /atm
0 124.7776
20 123.4774
40 122.8682
60 122.5827

a. What is the order of reaction with respect to CH3I?

Since the concentration of OH- is large, it can be assumed constant for the duration of the
reaction. Derive the equation relating the order of reaction to the reaction time and
concentration of reactants
1 = [CH3 I]1 [OH ]
2 = [CH3 I]2 [OH ]

1 [CH3 I]1
=( )
2 [CH3 I]2
 1 [CH3 I]1
ln ( ) = ( )
2 [CH3 I]2
2 [CH3 I]1
ln ( ) = ( )
1 [CH3 I]2

ln (2 )
= 1
[CH3 I]1
([CH I] )
3 2

Performing the calculations on any of the three temperatures shows that a=1; therefore, the
reaction is first order with respect to CH3I

b. At what temperature was the third set of data taken?

Since the reaction is determined to be first order in CH3I, the equation ln[A]= -kt + ln[A]0. should
form a linear plot. Using linear regression on the three data sets shows that
k(0 C)=0.1149 s-1
k(25 C)=0.6733 s-1
k(? C)=0.3443 s-1

Using the Arrhenius equation, an equation can be generated using k(0 C) and k(25 C).
1
= ( ) ( ) +

-Ea/R= -5759.8333 K
lnA= 18.9230

T when k=0.3443 s-1 is 288 K or 15.0C

c. What is the order of reaction with respect to OH-?

Given the balanced equation, for every moles of OH- consumed, moles of CH3I and moles of I-
are consumed and produced respectively. Therefore, the total concentration as a function of is
c0- where c0 is the initial concentration (5.1 M).

The integrated rate laws, however, are concerned with the amount of reactant remaining, not
consumed; therefore, the amount of OH- remaining must be calculated using [OH-]=[OH]0-
where [OH]0=0.1 M

t/s /atm c/M /M [OH-]/M

0 124.7776 5.10000 0 0.10000
20 123.4774 5.04685 0.05315 0.04685
40 122.8682 5.02196 0.07804 0.02196
60 122.5827 5.01029 0.08971 0.01029

Linear regression shows that a straight line is produced when ln[OH-] is plotted against t,
therefore the reaction is first order with respect to OH-

d. In the second experiment, what is the pH of the solution at t = 50 s?

The integrated rate law can be expressed as ln[OH-]=k(-t)+ln[OH-]0. Linear regression yields
k=0.03790 s-1 and ln[OH-]0=-2.3027. Substituting t = 50 s yields [OH-]=0.01503 M. Recall that
pOH=-log[OH-]=1.823 therefore pH=12.177.