Escolar Documentos
Profissional Documentos
Cultura Documentos
Chapter 15b
If X = E:
E is negative; then the system has used up some of the
stored energy
E is positive; then the system has increased it stored
energy
Expansion Work
A system can do two kinds of work: Expansion or Nonexpansion.
1. Expansion work the work of expansion against an
external force.
A = area
Substituting F in the work equation with P A :
Work = P A h
Volume of a cylinder = A h
V = A h
Work = P V
10
w = PV
The external
pressure ,
atmospheric
pressure, is the
force opposing
expansion.
The piston is
released and the
gas expands.
When a system
expands, it loses
energy as work.
When the V is
positive, w is
negative.
w = P V
11
12
1 Pa = 1 kg m 1 s 2
(1 Pa ) ( m3 )
1 kg 3
1 kg m
m ) =
2 (
s2
m s
= 1 joule
13
14
15
Heat
Heat
16
17
18
Heat
Heat
q > 0 if heat is absorbed by the system.
20
Heat
Surroundings
melting
Vaporization
Some chemical reactions
21
22
Exothermic process
Endothermic process
2NO (g)
24
NH4SCN plus
Ba(OH)2 8H2O is an
endothermic reaction
that causes
atmospheric H2O
vapor to freeze on the
outside of the beaker.
Internal Energy
25
26
Internal Energy
E = q + w
28
p.605
27
E surr = 400 J
E sys = E 2 - E1
E = E 2 - E1 = q + w
E = 1200 J + (-800 J)
E 2 = E1 + E sys
E = 400 J
= E1 + 400 J
E sys = + 400 J
29
30
If E = q, then E = + 1300 J
31
w = PV
or w = P (V2 V1)
force
F
Pressure is force per P =
= 2
area
d
unit area.
Volume is distance V = d 3
cubed.
PV is a work term, i.e., the same units are used for
energy and work.
F
P V = 2 d 3 = F d w hich is w ork
d
( )
33
E.g. (A closed system) Some dry ice is placed into a rigid flask,
which is then sealed.
As the dry ice absorbs heat from the surroundings, some of the
dry ice sublimes to form carbon dioxide gas.
34
CO2 ( s)
heat
CO2 ( g )
A system maintained at
constant volume can do no
expansion work.
35
36
38
3 mol gases
2 mol gases
P ( V ) = n g as R T
39
Fig. 15-7, p.606
40
When
1. V2 = V1
= ( n gas ) RT
Thus we can see that w = ( n gas ) RT
2. V2 > V1
at constant T and P.
3. V2 < V1
41
Then
Examples
V1
V2
PV = 0
ngas = 0
PV > 0
ngas > 0
PV < 0
ngas < 0
N
+ 3 H 2(g) 2 NH 3(g)
2(g)
2 mol gas
0 mol gas
4 mol gas
2 mol gas
1 mol gas
2 mol gas
42
2 NO( g ) + O 2( g ) 2 NO 2( g )
3 mol gas
1 mol gas
2 mol gas
2 mol gas
The increase in volume was a result of more moles of gas products than reactants.
The increase of gas products increases volume against constant pressure.
Consequently, w = PV < 0.
Work is done by the system on the surroundings. The internal energy of the system
decreases by the amount of work done by the system.
43
Relationship of H and E
Enthalpy
44
H = Hfinal Hinitial
H = Hsubstances produced Hsubstances consumed
45
Relationship of H and E
46
Relationship of H and E
48
Indicates the
release of energy
Indicates the
absorption of energy
H = 3.516 103 kJ
H = + 3.516 10 kJ
-or-
-or-
E = 3.516 103 kJ
E = + 3.516 103 kJ
49
Relationship of H and E
Relationship of H and E
When heat energy has been transferred to a constantpressure system, the enthalpy of the system increases by
that amount.
When heat energy has been released from constantpressure system, the enthalpy of the system decreases by
that amount.
50
52
Relationship of H and E
Example: Given that the combustion of n-pentane, nC5H12, at constant pressure releases 3523 kJ of heat at
a temperature of 298K., H = -3523 kJ/mol
What are the values of the work term and E for this
reaction?
8 mol of gas
53
5 mol of gas
54
Relationship of H and E
Relationship of H and E
E = q + w
H = 3523 kJ
w = + 7.422 kJ
8 mol gas
5 mol gas
E = ( 3523 kJ ) + ( +7.422 kJ )
= 3516 kJ
56
Relationship of H and E
Relationship of H and E
57
Spontaneous Changes
Spontaneous Changes
58
Have you ever seen rust turn into iron metal without
man made interference?
59
60
10
61
62
63
64
Gases are
distributed
evenly when
allowed to
expand into an
evacuated bulb.
65
66
11
If a system has several available states, the one state that has the
greatest number of microstates is the one that is most likely to occur.
67
68
Changes in Entropy
negative.
2. The entropy (disorder) of the universe must
increase.
Fundamentally, the system must be capable of
doing useful work on surroundings for a
spontaneous process to occur.
69
Changes in Entropy
Changes in Entropy
Example:
a) Calculate the change in entropy in 1.0 L of water at
0.oC when it absorbs 235 J of energy from a heater.
b) If the 1.0 L of water is at 99oC, what is the change in
entropy?
c) Explain any difference in entropy change.
S =
qrev
T
70
71
72
12
Changes in Entropy
Changes in Entropy
74
Changes in Entropy
75
Entropy, S
76
77
78
13
Entropy, S
79
1.
80
82
vap
Tb
83
84
14
H ofus
Tf
85
kJ
; T = 100. + 273 = 373 K
mol
J
The units of S are
K mol
H vap = 40.7
a)
S =
86
for C2 H 5OH =
C2 H 5OH
109 J
q H 40700 J / mol
=
=
=
373K
T
T
K mol
87
Entropy, S
88
89
90
15
91
92
4 CO molecule have 24
possible arrangements in a
crystal.
Since the crystal is not a
perfectly ordered array,
some positional disorder is
seen in the crystal-called
residual entropy.
93
94
95
96
16
97
Entropy, S
98
99
Entropy, S
100
Entropy, S
101
102
17
Entropy, S
Entropy, S
103
104
Entropy, S
43.2 J/ K mol
22.0 J/K mol
S surr =
OoC,
105
Entropy, S
H
T
T = 5.0 oC + 273 = 268K
S surr =
106
H fus =
6.01 kJ
( from Table 6.3)
mol
S surr =
108
18
Entropy, S
Entropy, S
109
Entropy, S
110
Entropy, S
In an exothermic
reaction:
In an exothermic
reaction:
112
Entropy, S
In an endothermic reaction:
the entropy of the system
increases while the entropy of
the surroundings decreases.
There can be an overall
increase in entropy if the
disorder of the system increases
enough.
S surr =
H
+ 49000 J
J
=
= 164.43
298 K
T
K
114
19
Entropy, S
Entropy, S
+ H and S
Under these conditions the process is absorbing heat
and becoming more ordered.
Under these conditions the process is decreasing the
entropy of the surroundings and decreasing the entropy
of the system.
Under these conditions, the total entropy change is
negative.
115
116
Entropy, S
Entropy, S
2 NO 2(g)
N 2 O 4(g)
S orxn =
n S
o
products
n S oreactants
n
N O
2 NO 2(g)
2 4(g)
118
Entropy, S
3 NO( g )
N 2 O( g ) + NO 2( g )
Entropy, S
S0298 =
S0N 2O(g) +
S0NO2(g ) 3 S0NO(g)
3 NO (g )
N 2 O (g ) + NO 2(g )
119
20
Determining S: Examples
Equilibrium
1.
2.
3.
4.
5.
6.
121
Equilibrium
122
Equilibrium
2
reverse
forward
2
reverse
123
Equilibrium
124
Equilibrium
forward
products
reactants
reverse
125
At equilibrium: Stot = 0
126
21
127
G = H - TS
Stot = S + Ssurr
128
H
at constant T and P
T
129
130
131
132
22
133
134
135
136
If
137
138
23
139
140
141
142
143
144
24
+
+
T dependent
T dependent
145
146
2219.9 ( 2108.5 ) kJ
So =
298 K
So = 0.374 kJ
= 374 J
K
K
147
148
H O
H2O(A )
2 (g)
Because this is an equlibrium process G = 0.
H
Thus H = TS and T =
S
149
150
25
assum e H @ B P H o298
o
H = H
o
H 2 O (g)
assume S @ BP S0rxn
o
H 2O ( l )
H o = [ 241.8 ( 285.8 ) ] J K
o
H = + 44 .0 kJ@ 25 C
151
152
H
H o
44 .0 kJ
=
= 370 K
0.1188 kJ K
S
So
370 K - 273 K = 97 o C
% error =
153
154
155
26