5

3 The second and third laws

3A Entropy
E3A.1(a) not spontaneous
E3A.2(a) +366 J +309 J
E3A.3(a) +3.1 J K−1
E3A.4(a) ∆S = +2.9 J K−1 ∆S sur = −2.9 J K−1 ∆S tot = 0 ∆S = +2.9 J K−1 ∆S sur = 0
∆S tot = +2.9 J K−1 ∆S = ∆S sur = ∆S tot = 0
E3A.5(a) 191 K
E3A.6(a) 24.1%
P3A.1 q = +2.74 kJ w = −2.74 kJ ∆U = 0 ∆H = 0 ∆S = +9.13 J K−1 ∆S sur =
−9.13 J K−1 ∆S tot = 0 q = +1.66 kJ w = −1.66 kJ ∆U = 0 ∆H = 0 ∆S =
+9.13 J K−1 ∆S sur = −5.54 J K−1 ∆S tot = +3.59 J K−1
P3A.3 VB = 2.00 dm3 VC = 3.19 dm3 VD = 1.60 dm3 q 1 = +215 J q 2 = 0 q 3 =
−157 J q 4 = 0 ∣w∣ = +58 J 27%
Th
P3A.5 ∣q∣ × ( − 1)
Tc

3B Entropy changes accompanying specific processes

E3B.1(a) +30 kJ mol−1
E3B.2(a) +87.8 J K−1 mol−1 −87.8 J K−1 mol−1
E3B.3(a) +4.55 J K−1 mol−1
E3B.4(a) 153 J K−1 mol−1
E3B.5(a) Tf = 298 K ∆S 1 = −31.0 J K−1 ∆S 2 = +33.7 J K−1 ∆S tot = +2.7 J K−1
E3B.6(a) −22.1 J K−1
E3B.7(a) +87.3 J K−1
P3B.1 ∆S = −21.3 J K−1 ∆S sur = +21.7 J K−1 ∆S tot = +0.4 J K−1 spontaneous ∆S =
+110 J K−1 ∆S sur = −111 J K−1 ∆S tot = −1.5 J K−1 not spontaneous
P3B.3 +10.7 J K−1 mol−1
m (Tc + Th )2
P3B.5 C p,m ln ( ) +22.6 J K−1
M 4(Tc × Th )
P3B.7 ∆S = +45.4 J K−1 ∆S = 0 J K−1 ∆S sur = +51.2 J K−1
P3B.9 +477 J K−1 mol−1
P3B.11 +7.5 × 102 J 6.11 × 103 J +6.86 kJ 68.6 s

3C The measurement of entropy

E3C.1(a) 4.8 × 10−3 J K−1 mol−1
6

E3C.2(a) −386.1 J K−1 mol−1 +92.6 J K−1 mol−1 −153.1 J K−1 mol−1
E3C.3(a) −99.38 J K−1
P3C.1 76.04 J K−1 mol−1
P3C.3 0.93 J K−1 mol−1 63.9 J K−1 mol−1 64.8 J K−1 mol−1 64.8 J K−1 mol−1 at 298 K
62.4 J K−1 mol−1 at 273 K
P3C.5 +42.08 J K−1 mol−1 +41.16 kJ mol−1 at 298 K +41.15 J K−1 mol−1 +40.8 kJ mol−1
at 398 K
P3C.7 89.0 J K−1 mol−1 at 100 K 173.8 J K−1 mol−1 at 200 K 243.9 J K−1 mol−1 at 300 K
a
P3C.9 a = 2.569 JK−4 mol−1 b = 2.080 JK−2 mol−1 S m (0)+ T 3 +bT 11.01 J K−1 mol−1
3

3D Concentrating on the system

E3D.1(a) ∆ r H −○ = −636.6 kJ mol−1 ∆ r G −○ = −521.5 kJ mol−1 ∆ r H −○ = +53.40 kJ mol−1
∆ r G −○ = +25.8 kJ mol−1 ∆ r H −○ = −224.3 kJ mol−1 ∆ r G −○ = −178.7 kJ mol−1
E3D.2(a) −480.98 kJ mol−1
E3D.3(a) 817.90 kJ mol−1
E3D.4(a) −522.1 kJ mol−1 +25.78 kJ mol−1 −178.6 kJ mol−1
E3D.5(a) −340 kJ mol−1
P3D.1 49.9 bar 900 K +50.7 J K−1 −11.5 J K−1 ∆U A = +24.0 kJ ∆U B = 0 +3.46 ×
103 J 0
P3D.3 -47 kJ mol−1
P3D.5 ∆ r G 1−○ = +965 kJ mol−1 ∆ r G 2−○ = −961 kJ mol−1 ∆ r G −○ = +4 kJ mol−1

3E Combining the First and Second Laws

E3E.1(a) −17 J
E3E.2(a) −36.5 J K−1
E3E.3(a) −85.40 J
E3E.4(a) +10 kJ +1.6 kJ mol−1
E3E.5(a) −1.6 × 102 J mol−1
E3E.6(a) +11 kJ mol−1
P3E.1 ∆ r G −○ (298 K) = −514.38 kJ mol−1 ∆ r H −○ (298 K) = −565.96 kJ mol−1 ∆G(375 K) =
−501 kJ mol−1
P3E.3 22 kJ mol−1
∂T ∂V ∂p ∂S ∂V ∂S
P3E.5 ( ) = ( ) ( ) =( ) ( ) = −( )
∂p S ∂S p ∂T V ∂V T ∂T p ∂p T
pf RT a
P3E.7 G m (p f ) = G m (p i ) + RT ln ( ) + b(p f − p i ) Vm = − G m (p f ) =
pi p pRT
pf a pf
G m (p i ) + RT ln ( ) − ln ( )
pi RT pi
 7

I3.1 −20.8 K +37.1 J K−1 mol−1

I3.3 +19.5 J K−1 mol−1