NS102 Spring 2015

Extra Study Questions for Midterm 1

(Climate Change Module)
GAS LAWS

1) A 60.0 L tank of chlorine gas at 27 °C and 125 atm springs a leak. When the leak was discovered, the pressure
was reduced to 50 atm. How many moles of chlorine gas escaped?
Ans:

PV=nRT
-2​
125 atmx60L=nx8.2x10​ Latm/molKx(273+27)K
n=304 mol

-2​
50 atmx60L=nx8.2x10​ Latm/molKx(273+27)K
n=121 mol

304-121= 183 moles of chlorine escaped

2) 1 mol of Argon confined in a volume of 0.1 L exerts a pressure of 1070 atm at 1000K. The van der Waals
2​ -2​
equation parameter due to molecular interactions is 1.35 L​ atm mol​ .
(a) Estimate the value of the parameter due to excluded volume.
23​
(b) Estimate the radius of one Argon atom (one mole has 6 x 10​ particles).
-9​
(c) The actual atomic radius of Argon is 0.98 Å (1 Å = 10​dm). What is the percent error in your estimation in
part (b)?
(d) Do you expect a better or worse estimation of the radius at 100 atm? Why?

Reminders:
­ L and dm​ 3​
are the same thing!
­ R​ = 8.314 J mol​-1​ -1​ -1​ -1
K​= 0.082 atm L mol​ K​
­ The van der Waals equation of state is →

(a) Substitute values into the vdW eq to get: b=0.032 L/mol

(b) I mol of Argon takes up 0.032 mol space, a single Argon then takes up 0.032/6.02x1023​
​L =
5.32x10­26
​​L = 53.2 Å3​
​(the last step is because 1 L = 1 dm3​
​= 1027​
​Å3​)
​
Assuming spherical molecule: 53.2 Å3​ 3​
​= 4/3π R​→​
​ R = 2.3 Å.
(c) % error = (2.3 – 0.98) / 0.98 x 100 = 138 %
(d) This question is not well posed. Let’s assume, the question says you measure P,V,T at lower
pressure, then recalculate b – then the equation will probably work better since as we push
molecules further together, simple corrections like that in vdW eqn of state will work better, so the
prediction will be better.

FIRST LAW
3​ 3​ o​
3) Consider the expansion of 1 mol of an ideal gas from 0.01 m​to 0.1 m​at 25​C by three different processes
given below and calculate work at each step.
(a) against a constant external pressure of 0.1 bar
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 3 3
(b) from 0.01 m​ to 0.025 m​ against a constant external pressure of 0.333 bar, followed by a second
3 3
expansion from 0.025 m​to 0.05 m​ against a constant pressure of 0.2 bar, followed by a third expansion
3​ 3​
from 0.05 m​to 0.1 m​against a constant pressure of 0.1 bar
(c) a reversible expansion

5​
ANS: Conversion: 1 bar = 10​Pa a) = -900 J b) = -1500 J c) = -5700 J

5​
Conversion: 1 bar = 10​Pa

a) w = -P​ Δ​
​
ext​
5​
V = 0.1x10​ 3​
x0.09 =900 Pa.m​= -900 J
5​ 5​ 5​
b)-[ (0.333x10​x0.015)+(0.2x10​x0.025)+(0.1x10​x 0.05)] = -1500 J
3​ 3​
c) w= -nRTln(V​-V​
f​ ) = -(1 mol)(8.314J/K/mol)(298 K) ln(0.1 m​
i​ /0.01m​) = -5700 J

** w is path dependent**

4) A gaseous mixture was enclosed in a piston and cylinder system having a volume of 1200 ml. When a chemical
reaction occurred, the volume decreased to 456 ml and 235 calories of heat was absorbed. The external
pressure was 742 mmHg. Calculate the change in enthalpy, work and the change in internal energy for this
system in kJ.

ANS: ΔH= q​= 0.983 kJ

p​ w = 0.0727 kJ ΔU = 1.0557 kJ

At constant P; ​ q​
ΔH= ​ =235 cal x 4.18J/1 cal=983 J=0.983 kJ
p​
w= ­P​
ΔV= -742mmHgx 1atm/766 mmHg x(0.456 L-1.2L)= 0.720 L.atm
3​
0.720 L.atm=0.720L.atmx101.3J/1 L.atmX1kJ/10​ J =0.072 kJ
ΔU=q+w= ​ 0.983 kJ+​
0.072 kJ= 1.055 kJ

SECOND LAW

5) One mole of an ideal gas at a temperature of 300 K is expanded isothermally to three times its initial volume.
(a) To what temperature should it be cooled at constant volume to restore its entropy to its initial value?
(b) What is the amount of work done throughout the whole cycle?
(c) What is the change in the internal energy of the system upon completion of these processes?
c​
Take molar ​ R​
v​= 5​/2.

a) For the reversible isothermal expansion of an ideal gas:

V
∆S = N Rln V f
i

For the constant volume process in an ideal gas:

The sum of the two equations should be zero (entropy change in the second step should be negative of
that in the first step):

∆Si =− ∆Sf
V T
N Rln V f =− N cvln T f
i
T i
ln3 =− 2.5ln 300f
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 T​= 193 K
f​

b) Work = ­P​ dV; in the second step, there is no volume change, so no work; in the first step:
ext​

W = ­1 mol x (8.314 J/mol/K) x 300 K (ln 3) = ­2740 J

c) For ideal gas, in the first step at constant temperature there is no internal energy change, since U is
only a function of temperature; in the second step at constant volume we have
ΔU = N C​ ΔT = 1 mol x 2.5 x (8.314 J/mol/K) x (193­300)K = ­ 2224 J
v​

So the system loses ­2224 J of energy ; 2740 of this is used to do work, 516 J is taken in as heat..

6) A sample consisting of 1 mol of an ideal gas is taken through the cycle above in the order A→B→C. Compute
Q​
,​W​,​U​
Δ​ Δ​
,​ H​
, and ​S​
Δ​ for each step, and for the overall cycle. Write your answers in the table below. If the
numerical answer cannot be obtained from the given information, then write in the sign of the quantity, or ?
as appropriate. Show your work on the reverse side.

step Q W Δ​
U Δ​
H Δ​
S
A→B
B→C
C→A
overall

Note that T​ B​= T​= 2T​

c​ from ideal gas law; also C​
A​ -C​
P​ = R for an ideal gas;
v​
Finally, for state functions the overall cycle should give 0 change
step Q W Δ​U Δ​
H Δ​S
A→B C​ (T​ -T​
v​ B​ A​ ): ​
+ve 0 C​ (T​-T​
v​ B​ A​):​+ve Δ
=​ ​
U​
+ Δ
​ P​
(​V): N C​
v​ 2:​
ln +ve
+ve
B→C Using Q+W=​ Δ​U=​ RT​ ln2:
B​ -RT​ln
B​ 2: ​
- ve 0 0 R ln 2:​
+ve
+ve
C→A C​ (T​
P​ -T​
A​ ): ​
C​ -ve ∙​
20 L​atm: ​ +ve -ve =Q : ​-ve -N C​ln 2:​
P​ -ve
overall RT​ (ln2-2): ​
B​ -ve ? 0 0 0

o​ o​
7) Two identical blocks of iron, one at 100​C and the other at 0​C, are brought into thermal contact. What
happens? What is the total entropy change? (Assume the heat capacity of each block,​ c​
, is constant over this
temperature range, and neglect volume changes)
Δ​
ANS: Total entropy change : ​S = 0.024​
c

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 GIBBS ENERGY

8) Consider the reaction of nitrogen monoxide and chlorine to form nitrosyl chloride:
2NO (g) + Cl​(g) → 2NOCl(g)
2​

o​
Δ​
G​ = 66.2 kJ/mol
f​(NOCl(g))​
o​
Δ​​(NO)​= 86.6 kJ/mol
Gf​

Δ​
(a) Calculate ​ ​for the reaction.
Go​
(b) Calculate Δ
​​
G when p​NO =
​ 0.3 atm, p​ = 0.1 atm, and p​
Cl2​ = 0.45 atm
NOCl​

​
Ans: Δ​
a) ​Go​
= -40.8 kJ Δ​
b) Q = 23, ​G = -33.0 kJ

9) Consider the following reaction:

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 (a) Δ​
G = +200 kJ/mol & Activation Energy = +400 kJ/mol for the forward reaction. Please circle the energy
curve shown below (​ R​ = reactants, ​ P ​
= products) that best represents the reaction described above.
Explain your reasoning to justify your choice.

Δ​
Circle both the second and third figs – in both ​G is negative and there is a barrier

(b) The reaction is non-spontaneous at room temperature. Please suggest one thing you can change that
should increase the rate of reaction ​and ​make the reaction more spontaneous. Clearly discuss how this
change will influence the rate of reaction and why it will affect the thermodynamics (spontaneity) of the
reaction.

T​
Increasing ​ Δ​
in the ​ G=​ Δ​ Δ​
H – T​ Δ​
S expression will make ​ G​more negative, and the forward reaction will be more spontaneous.
Increasing the ​T​will also make it easier for the molecules to collide, hence increasing the rate.

PHASE CHANGES

10) In the following graph, the Gibbs free energy is shown as a function of either temperature or pressure. Given
d​
the general equation ​ G​ =​V​d​
P​–​S​d​
T​as a reminder, answer the following:
(a) What variable should be on the x-axis? Label on figure. ​Since the slopes are negative, it must be T
(b) What variable is being kept constant? ​Pressure
(c) For a stable system, what lines are expected to be traced on the figure? Show VERY CLEARLY on the figure.
Shown in ​green​ on figure
(d) What phase does each of the curves correspond to? Show VERY CLEARLY on the figure.
(e) Show the point(s) of expected phase transitions, and say what type of a phase transition it is
(condensation, melting, sublimation, etc.). ​
Shown in ​blue​on figure

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 11) Using the following phase diagram, and starting at 5 bar and 1 K, describe the
changes you would observe as you (a) first increase the pressure to 80 bars at
constant temperature, (b) then increase the temperature to 3 K at constant
pressure, (c) then directly decreasing the pressure to 0.01 bar, and increasing the
temperature to 4.5 K simultaneously, (d) finally, directly decreasing the
temperature to 1 K at constant pressure.
(a) from the liquid helium-II (superfluid) phase, it shifts to solid He.
(b) from the solid phase, it shifts o liquid He-I phase.
(c) it now shifts to the gas phase.
(d) finally ends up at the initial phase.

KINETICS

12) For the reaction: NO​ Cl(g) + NO (g) → NO​

2​
10​
(g) + ONCl(g), the pre-exponential factor A is 1x10​
2​ and the energy
of activation is 40 kJ/mol. The rate equation is first order in NO​Cl
2​ and second order in NO.

k​
(a) What is the rate constant, k, at 500 K? Make sure you put the correct units for ​.

k​ 10 ​ -40000J/mol/(8.314 J/molKx500K) ​
= 10​ e​ 5 ​ -2​-1
= 6.6x10​ M​ s​

(b) What is the rate of the reaction at this temperature, if 0.1 M of NO​Cl is reacted with 0.2 M of NO?
2​

2​ 5 ​ -2​-1​ 2​ 2​
Rate = k [ NO​Cl ] [ NO ]​
2​ = 6.6x10​ M​ s​x 0.1 M x 0.2​M​= 2640 M/s

(c) What is the overall order of the reaction?

rd​
3​ order.

(d) Could this reaction be an elementary reaction? Explain.

nd​
It cannot, because if it were, then the rate equation would have been first order in both reactants, and 2​ order
overall.

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 GREENHOUSE EFFECT

13) Mars orbits the Sun at a distance of 1.52 AU (1 astronomical unit is defined as the average distance from Earth
2​
to the Sun, approximately 93 million miles). The solar flux incident on a planet is given by S​ = S​
planet ​ /R​
sun​ where
2​
R is the distance between the Sun and planet and has units of AU. Solar flux incident on Earth is 1367 W/m​ .

(a) What is the solar flux of Mars?

(b) If Mars has an albedo of 0.22, calculate the effective radiative temperature.
(c) If the mean surface temperature of Mars is measured to be 218 K, calculate the greenhouse effect in K.

(a) Solar flux of Mars:

2​ 2​
S​ = 1367 x 1/(1.52)​
mars​ = 593 W/m​.
4​
(b) T​= 593/4/(5.67x10^-8)x(1-0.22) : T = 212.5 K
(c) 218 – 212.5 = 5.5K

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