Exercise 1: Thermodynamics: A Review

Exercise 1
THERMODYNAMICS: A Review
OBJECTIVES

Upon completion of the experiment, the student should be able to:

1. recall basic concepts and terminologies in thermodynamics;
2. solve problems in thermodynamics, i.e. calculation of enthalpy change of a reaction,
heat evolved in a reaction, specific heat capacity and molar heat capacity of a substance,
standard enthalpy of formation; and
3. tell whether a reaction is spontaneous or non-spontaneous, exothermic or endothermic
given the thermodynamic parameters.
PART I. Matching. Match the thermodynamics terms with its definition or description by
placing the corresponding letter in the space provided.

__T__ 1. Calorimetry C. One that proceeds on its own without any

continuous external influence
__G__ 2. Closed system D. The sum of kinetic and potential energies for
each particle in a system
__A__ 3. Endothermic E. The enthalpy change for a reaction
F. A system that freely exchanges energy and
__N__ 4. Enthalpy change (ΔH) matter with its surroundings
G. A system that exchanges only energy with its
__R__ 5. Entropy (S) surroundings, not matter
H. A system that does not exchange energy or
__B__ 6. Exothermic matter
I. The energy transferred from one object to
__J__ 7. First law of thermodynamics another as the result of a temperature
difference between them
__I__ 8. Heat (q) J. Energy cannot be created or destroyed, it can
only be converted from one form into another.
__L__ 9. Heat capacity (C) __S__ 11. Hess’s law

__D__ 12. Internal energy (U)

__E__ 10. Heat of reaction

__H__ 13. Isolated system

A. A reaction in which heat is absorbed and the
temperature of the surroundings falls __M_ 14. Molar heat capacity
B. A reaction in which heat is evolved and the
temperature of the surroundings rises __F__ 15. Open system

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 Exercise 1: Thermodynamics: A Review

M. The amount of heat necessary to raise the

__K__ 16. Specific heat (s) temperature of 1 mol of substance by 1°C
N. The heat change in a reaction or process at
constant pressure
O. A function or property whose value depends
__C__ 17. Spontaneous process only on the present condition of the system,
not on the path used to arrive at that condition
__O__ 18. State function (Examples in thermodynamics are H, U, G and
S)
__P__ 19. System P. The specific part of the universe that is of
interest in the study (surrounding is everything
else, the rest of the universe)
__Q__ 20. Temperature Q. A measure of the kinetic energy of molecular
motion
R. The amount of molecular randomness in a
(ΔUsys + ΔUsurrounding = 0). The total internal system
energy of an isolated system is constant (ΔU sys = S. The overall enthalpy change for a reaction is
q + w). equal to the sum of the enthalpy changes for
K. The amount of heat necessary to raise the the individual steps in the reaction.
temperature of 1 gram of substance by 1°C T. The process of measuring the amount of heat
L. The amount of heat necessary to raise the released or absorbed during a chemical
temperature of a given quantity of the reaction
substance by 1°C

PART II. Numeric Response. Solve the following review questions clearly and neatly. Show all
your solutions. Box your final answers with appropriate units.

Heat, Work, and Energy

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Exercise 1: Thermodynamics: A Review

1. A reaction takes place at a constant pressure of 1.10 atm with an internal energy change
(∆ U ) of 71.5 kJ and a volume decrease of 13.6 L. What is the enthalpy change (∆ H ) for
the reaction? (1 L∙ atm=101.325 J ¿

Given:
P=1.10 atm
∆ U =71.5 kJ
∆ V =13.6 L
∆ H =?

Formula:
∆ H =∆ U + P ∆ V
∆ H =enthalpy change( kJ )
∆ U =internal energy change (kJ )
P= pressure( atm)
∆ V =volume change( L)

Solution:
P ∆ V = (1.10 atm )( 13.6 L )
¿ 14.96 atm ∙ L
¿(−14.96 atm∙ L) ( 101.325 J
1.0 atm ∙ L )( 1000
1 kJ
J)
P ∆ V =−1.515822kJ

∆ H =∆ U + P ∆ V
¿ 7 1.5 kJ −1.515822 kJ

∆ H =69.984178 kJ ≈ 69.98 kJ

2. Aluminum metal reacts with chlorine with a spectacular display of sparks:

o
2 Al (s) +3 Cl2 (g) →2 AlCl 3 (s) ∆ H =−1,408.4 kJ
How much heat in kJ is released on reaction of 5.00 g of Al?

Given:
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Exercise 1: Thermodynamics: A Review

g
∆ H o=−1408.4 kJ M Al=26.98
mol
m Al=5.00 g
n Al =2.00 mol
q=?

Formula:

( )( )
o
mass ∆H
q=
molar mass moles

(
¿ ( 5.00 g of Al ) )(
1 mol of Al −1,408.4 kJ
26.98 g of Al 2 mol of Al )
q=−130.50 kJ
¿(130.50 kJ of heat is released .)

Calorimetry and Heat Capacity

3. Titanium metal is used as a structural material in many high-tech applications, such as in

J
jet engines. What is the specific heat of titanium in if it takes 89.7 J to raise the
g∙℃
temperature of a 33.0 g block by 5.20°C? What is the molar heat capacity of titanium in
J
?
mol ∙℃

Given:
g
q=89.7 J M Ti =47.88
mol
mblock =33.0 g
∆ T =5.20 ℃
C p=?
C n=?

Formula:
q
C p=
m ∆T

C n=M C p

J
C p=specific heat( )
g ∙℃
J
C n=molar heat capacity( )
mol ∙ ℃

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Exercise 1: Thermodynamics: A Review

g
M =molar mass ( )
mol
q=heat (J )
m=mass( g)
∆ T =change∈temperature (℃)
Solution:
q
C p=
m ∆T
89.7 J
¿
(33.0 g)(5.20℃)
J J
C p=0.5227272727 ≈ 0.52
g∙℃ g∙℃

C n=M C p
¿( )(
47.88 g 0.5227272727 J
1.0 mol g∙℃ )
J
C n=25.03
mol ∙℃

4. When a solution containing 8.00 gof NaOH in 50.0 g of water at 25.0 ° C is added to a
solution of 8.00 g of HCl in 250.0 g of water at 25.0 °C in a calorimeter, the temperature
of the solution increases to 33.5 °C. Assuming that the specific heat of the solution is
J
4.184 and that of the calorimeter absorbs a negligible amount of heat, calculate
g∙℃
∆ H in kJ for the reaction:

NaOH (aq) + HCl(aq) → NaCl(aq) + H 2 O(l)

Given:
Solution 1
mNaOH =8.00 g
mH O =50.00 g
2

T H O=25.0℃
2

Solution 2
mHCl =8.00 g
mH O =250.0 g
2

T H O=25.0℃
2

∆ T 1 ,2=33.5 ℃
J
C p=4.184
g ∙℃

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Exercise 1: Thermodynamics: A Review

Formula:
∆ H =mC p ∆ T
q=heat (J )
m=mass( g)
C p=specific heat ( g ∙J℃ )
∆ T =change∈temperature (℃)

Solution:
∆ H =mC p ∆ T
J
¿( 8 g NaOH +8 g HCl +50 g H O +250 g H O )(4.184 ) ¿)
2 2
g∙℃
J
¿(316 g)( 4.184 )¿)
g∙℃
¿ 11,238.224 J
¿(11,238.224 J ) ( 1000
1kJ
J)
∆ H =11.238224 kj ≈ 11.24 kJ

Hess’s Law and Heats of Formation

5. Sulfuric acid ( H 2 SO4 ¿, the most widely produced chemical in the world, is made by a
two-step oxidation of sulfur to sulfur trioxide, SO 3, followed by the reaction with water.
kJ
Calculate ∆ H of for SO 3(g) in , given the following data:
mol
S(s) +O 2(g ) → SO 2 (g) ∆ H o =−296.8 kJ
1 o
SO 2(g) + O → SO 3(g ) ∆ H =−98.9 kJ
2 2 (g)

Solution:
o
S(s) +O 2(g ) → SO 2 (g) ∆ H =−296.8 kJ
1
SO 2(g) + O → SO 3(g ) ∆ H o=−98.9 kJ
2 2 (g)

3
S(s) + O → SO 3 (g) ∆ H o =−395.7 kJ
2 2(g )

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Exercise 1: Thermodynamics: A Review

6. Acetic acid (CH 3 CO 2 H ), whose aqueous solutions are known as vinegar, is prepared by
reaction of ethyl alcohol (CH 3 CH 2 OH ) with oxygen:
CH 3 CH 2 OH (l) +O2 ( g) →CH 3 CO2 H(l) + H 2 O (l)
o o
Use the following ∆ H f values to calculate the ∆ H rxn in kJ:
kJ kJ kJ
CH 3 CH 2 OH (l )=−277.7 ; CH 3 CO 2 H ( l)=−484.5 ; H 2 O (l)=−285.8
mol mol mol

Formula:
∆ H rxn =(∑ ∆ H f ( product) ) −(∑ ∆ H f (reactant) )
o o o

Solution:
∆ H rxn =(∑ ∆ H f ( product) ) −(∑ ∆ H f (reactant) )
o o o

[[ (
¿ (1 mol ) −484.5
kJ
mol )] [ (
+ ( 1 mol ) −285.8
kJ
mol )]]−[ ( 1mol ) (−277.7 mol
kJ
)]
o
∆ H rxn =−492.60 kJ

Free Energy and Entropy

7. Tell whether the reactions with the following values of ΔH and ΔS are spontaneous of
non-spontaneous and whether they are exothermic or endothermic. Show you
calculations.
spontaneous or exothermic or
non-spontaneous endothermic
a . ∆ H =−48 kJ ; ∆ S=+135 J / K at 400 K spontaneous exothermic
b . ∆ H =−48 kJ ; ∆ S=−135 J / K at 400 K non-spontaneous exothermic
c . ∆ H=+ 48 kJ ; ∆ S=+135 J / K at 400 K spontaneous endothermic
d . ∆ H=+ 48 kJ ; ∆ S=−135 J / K at 400 K non-spontaneous endothermic

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Exercise 1: Thermodynamics: A Review

Formula:
∆ G=∆ H−T ∆ S

a. Given: ∆ G=−102 kJ
∆ H =−48 kJ ¿and ¿ at allT yield ¿ and is
∆ S= 135
J
( 1kJ
K 1000 J )(
=0.135
kJ
K ) spontaneous

T =400 K ∆ H =−48 kJ
Solution: ¿
kJ
∆ G=(−48.0 kJ )−(400.0 K )(0.135 )
K
∆ G=−102 kJ

b. Given: ∆ G=6 kJ
∆ H =−48 kJ ¿and ¿ at highT yield ¿ and is non-
spontaneous

∆ H =−48 kJ
¿

(
∆ S= −135
J
K )( 1000
1 kJ
)J =−0.135 kJK
T =400 K
Solution:
kJ
∆ G=(−48.0 kJ )−(400.0 K )(0.135 )
K
∆ G=6 kJ

c. Given: ∆ G=−6 kJ
∆ H =48 kJ ¿and ¿ at highT yield ¿ and is
(
∆ S= 135
J
K )( 1000
1kJ
)J =0.135 kJK spontaneous

T =400 K
Solution: ∆ H =48 kJ
kJ ¿
∆ G=( 48.0 kJ )−(400.0 K )(0.135 )
K
∆ G=−6 kJ

d. Given: ∆ G=102 kJ
∆ H =48 kJ ¿and ¿ at allT yield ¿ and is non-
T =400 K spontaneous
Solution:
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Exercise 1: Thermodynamics: A Review

kJ
∆ G=( 48.0 kJ )−(400.0 K )(−0.135 )
K
∆ G=102 kJ

8. Suppose that a reaction has ∆ H =−33 kJ and ∆ S=−58 J / K . At what temperature, if

any, will it change between spontaneous and non-spontaneous?

Given:
∆ H =−33 kJ

(
∆ S= −58
K
J
)( 1000
1 kJ
)J =−0.058 kJK
Formula:
∆H
∆ S=
T
∆H
T=
∆S

Solution:
∆H
T=
∆S
−33 kJ
¿
kJ
−0.058
K

T =568.9655 K ≈568.97 K

9. Suppose that a reaction has ∆ H =+41 kJ and ∆ S=−27 J / K . At what temperature, if

any, will it change between spontaneous and non-spontaneous?

Given:
∆ H =41 kJ

(
∆ S= −27
J
K )( 1000
1 kJ
)J =−0.027 kJK
Formula:
∆H
∆ S=
T
∆H
T=
∆S

Solution:
∆H
T=
∆S
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Exercise 1: Thermodynamics: A Review

41 kJ
¿
kJ
−0.027
K
T =−1,518.519 K ≈−1,518.52 K

10. Chloroform has ∆ H vaporization =29.2kJ /mol and boils at 61.2 °C. What is the value of
∆ S vaporization for chloroform?

Given:

(
∆ H vaporization = 29.2
mol )(
kJ 1000 J
1 kJ )
=29,200
J
mol
T =61.2 ℃+273.15=334.35 K
∆ S vaporization =?
Formula:
∆ H vaporization
∆ S vaporization =
T

Solution:
J
29,200
mol
∆ S vaporization =
334.35 K

J
∆ S vaporization =87.33
mol ∙ K

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