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1
JOULE’S EXPERIMENT
2
INTERNAL ENERGY (U)
the internal energy of a system is the total energy
contained within the system
INTERNAL ENERGY
U= Q + W (2.1)
Convention
• Positive when Q or W is
transferred to the system
• Negative when Q or W is
transferred from the system
4
For a closed system undergoing a process
that causes no change in the system other
than in its internal energy:
dUt = dQ + dW (2.3)
5
An alternative means of expression for the
extensive properties of a homogeneous system:
Vt = n V dan Ut = n U
(nU) = n U = Q + W
d(nU) = n dU = dQ + dW
6
The equations of thermodynamics are often
written for a representative unit amount of
material, either a unit mass or a mole.
For n = 1 the previous equations:
U = Q + W (2.4)
dU = dQ + dW (2.5)
7
PROPERTY
Property is an entity to describe a system
in equilibrium.
8
PROPERTY
EXTENSIVE INTENSIVE
n Vt
(specific volume) V
m
Vt
Vt (molar volume) V
n
9
Extensive property:
mass, total volume, length, and total
charge.
10
State of a system is the condition of the
system as represented by its properties
with respective values.
11
• from experience that for a homogeneous
pure substance fixing two of these
properties automatically fixes all the others,
and thus determines its thermodynamic
state.
12
• If this gas is heated or cooled,
compressed or expanded, and then
returned to its initial temperature and
pressure, its intensive properties are
restored to their initial values.
13
T2 = 600 K V2 = 49.90 L/mole
P2 = 1 bar U2 = 12563.1 J/mole
T1 = 300 K T4 = 300 K
P1 = 1 bar P4 = 1 bar
V1 = 24.938 L/mole V4 = 24.938 L/mole
U1 = 6222.7 J/mole U4 = 6222.7 J/mole
16
EQUILIBRIUM
18
T1 T2
P (T1) (T2)
1 2
P1 = P2
process
V1 V2 V 19
REVERSIBLE PROCESS
20
Reversible expansion of a gas
21
RESUME
A reversible process:
• Frictionless;
• The change from equilibrium is infinitesimal;
• Through a series of equilibrium;
• Caused by infinitisimal force imbalance;
• Its direction can be reverted at any point by an
infinitesimal external change/imbalance.
• When the direction is reverted, the process will
follow the same path and reach the initial
condition of the system and the surrounding.
22
EXAMPLE 2.1
A horizontal piston/cylinder arrangment is placed in a
constant-temperature bath. The piston slides in the
cylinder with negligible friction, and an external force
holds it in place against gas pressure at 14 bar. The
initial gas volume gas is 0.03 m3. The external force on
the piston is reduced gradually, and the gas expands
isothermally as its volume doubles. If the volume of the
gas is related to its pressure so that PVt = constant,
what is the work done by the gas in moving the
external force?
How much work would be done if the external force
were suddenly reduced to half its initial value instead of
being gradually reduced?
23
P
Vtawal Vtakhir Vt 24
PENYELESAIAN
dW P dV t
V2t
W dW P dV t
V1t
k
PV =k t
P t
V
V2t
dV t V2t
W k t k ln t
V1t V V1
Dengan:
14 10 5 N m2 0,03m3
t t
k PV P1 V1
42.000Nm 42.000 J
Maka:
V2t t t
dV V
W k t k ln 2
t
V1t V V 1
26
Tekanan akhir = k 42.000
P2 t 700.000 Pa 7 bar
V2 0,06
P
P1
P Vt = k
P2
V1t V2t
27
Pada kasus kedua, P gas turun mendadak menjadi 7 bar.
V1t V2t
29
PROSES DENGAN V KONSTAN
d(nU) = dQ + dW
dW = P d(nV)
dQ = d(nU)
Q = n U
Untuk n = 1 Q = U (2.8b)
31
PROSES DENGAN P KONSTAN (PROSES ISOBARIS)
dQ = d(nU) + P d(nV)
H U + PV (2.9a)
32
Persamaan di atas dapat ditulis sebagai:
dQ = d(nH)
Q = n H
Untuk n = 1 Q = H (2.9b)
33
KAPASITAS PANAS
U
Cv (2.11)
T V
34
Untuk sistem tertutup yang mengalami proses pada V
konstan:
dU = CV dT (V konstan)
T2
U CV dT (V konstan)
T1
PV
konstan
T
38
PENYELESAIAN
PV = k
2 4
Pb (soal a)
(soal b)
1
(1 bar) Pa
3 T = 298 K
V2 = V3 V1 = V4
39
P
2
298
1
3
V
40
a) Proses pendinginan pada P konstan (1 3) diikuti
dengan pemanasan pada V konstan (3 2)
PV P1V1 P2V2
konstan
T T1 T2
T1 = T2 P1V1 = P2 V2
P1 1 3
V2 V1 0,02479 0,004958 m mol
P2 5
41
2
P1V1 P3V3 P2 4
T1 T3
P1 = P3 P1 3 1
V1 V3 V2
V2 V1
V2 = V3 T1 T3 T3
V2 0,004958
T3 T1 298,15 59,63 K
V1 0,02479
42
Pendinginan pada P konstan (1 3)
Q = H = CP T = CP (T3 – T1)
= (29,10 J/mol/K) (59,63 – 298,15)K = 6.941 J/mol
H = U + PV H = U + (PV)
U = H – (PV) = H – P V = H – P (V3 – V1)
= – 6.941J/mol – (1 105) (0,004958 – 0,02479) J/mol
= – 4.958 J/mol
U = Q + W
W = U – Q = (– 4.958 + 6.941) J/mol = 1.983 J/mol
43
Pemanasan pada V konstan (3 2)
2
H = U + (PV) = H + V P P2 4
V2 V1
U = Q + W
45
b) Proses pemanasan pada V konstan (1 4) diikuti
dengan pendinginan pada P konstan (4 2)
2
P2 4
P1V1 P4V4
T1 T4
V1 = V4 P1 P4 P2 P1 3 1
P4 = P2 T1 T4 T4 V2 V1
P2 5
T4 T1 298,15 1.490,75 K
P1 1
46
Proses pemanasan pada V konstan (1 4)
Q = U = CV T
= (20,78) (1.490,75 – 298,15) = 24.788 J
U = Q + W W = U – Q = 0
H = U + (PV) = U + V P
= 24.788 + 0,02479 (5 – 1) 105 = 34.704 J
47
2
Pendinginan pada P konstan (4 2) P2 4
Q = H = CP T
= (29,10) (298,15 – 1.490,75) P1 3 1
= – 34.704 J V2 V1
U = H – (PV) = H – P V
= – 34.704 – (5 105) (0,004958 – 0,02479)
= – 24.788 J
U = Q + W
W = U – Q = – 24.788 + 34.704 = 9.914 J
48
Untuk keseluruhan proses
Q = 24.788 – 34.704 = - 9.916 J
W = 0 + 9.914 = 9.914 J
U = 24.788 – 24.788 = 0 J
H = 34.704 – 34.704 = 0 J
49
CONTOH 2.3
Hitung H dan U untuk udara yang mengalami per-
ubahan dari keadaan mula-mula 40F dan 10 atm ke
keadaan akhir 140F dan 1 atm. Anggap bahwa untuk
udara berlaku:
PV
konstan
T
Pada 40F dan 10 atm, volum molar udara V = 36,49
(ft3) (lb mol)-1. Kapasitas panas udara dianggap
konstan, CV = 5 dan CP = 7 (Btu) (lb mol)-1 (F)-1.
PENYELESAIAN
TA = 40F = (40 + 459,67) R = 499,67 R
Untuk memudahkan, P
maka proses dibagi 2: (atm) a
a. Pendinginan pada V
konstan (A-B)
B b C
b. Pemanasan pada P 1
konstan (B-C)
hingga dicapai kondisi VA V VC
akhir.
51
PA VA 10 36 ,49
k k 0 ,7303
TA 499 ,67
PB VB PB VB 1 36 ,49
k TB 49 ,97 R
TB k 0 ,7303
PC VC TC 599 ,67
k VC k 0 ,7303
TC PC 1
437 ,93 ft 3 lb mol
1
LANGKAH a:
KESELURUHAN PROSES:
53
PERHITUNGAN PROSES UNTUK GAS IDEAL
• U = U(T, P)
• P akibat dari gaya antar molekul U = U(T)
• Tidak ada gaya antar molekul
U dU
CV CV T (2.11)
T V dT
54
Entalpy untuk gas ideal:
H U + PV = U(T) + RT = H(T)
H dH
CP CP T (2.14)
T P dT
CP = CV + R (2.16) 55
Untuk perubahan yang dialami oleh gas ideal:
Takhir
dU = CV dT U CV dT (2.17)
Tawal
Takhir
dH = CP dT H C P dT (2.18)
Tawal
56
(Rabu, 13-3-2019)
57
Untuk gas ideal dalam sistem tertutup yang mengalami
proses reversibel:
dQ + dW = dU (2.5)
Jika digabung dengan pers. (2.11) maka:
dQ + dW = CV dT (2.19)
Sehingga: dQ = CV dT + P dV (2.20)
58
Takhir
H CP dT
Tawal
Takhir
U CV dT
Tawal
W P dV
dQ = CV dT + P dV
59
Jika P dieliminir dari persamaan
RT dQ = CV dT + P dV
P
V
dV
dQ C V dT RT (2.21)
V
dV
dW RT (2.22)
V
60
Jika V dieliminir dari persamaan
RT R RT
V dV dT 2 dP
P P P
R RT
dQ C V dT P dT 2 dP
P P
RT RT
CV dT R dT dP CV R dT dP
P P
dP
dQ CP dT RT (2.23)
P
dP
dW R dT RT (2.24)
P 61
Jika T dieliminir dari persamaan dQ = CV dT + P dV
PV V P
T dT dP dV
R R R
V P
dQ CV dP dV P dV
R R
CV V CV P CV V P
dP dV P dV dP CV R dV
R R R R
CV CP
dQ V dP P dV (2.25)
R R
dW P dV (2.26) 62
dU = CV dT (2.17)
dH = CP dT
(2.18)
dQ C V dT RT
dV
(2.21) dV (2.22)
dW RT
V V
dP dP
dQ CP dT RT (2.23) dW R dT RT (2.24)
P P
dQ
CV
V dP
CP
P dV (2.25) dW P dV (2.26)
R R
63
PROSES ISOTERMAL (dT = 0)
Dari pers. (2.17) dan (2.18):
U = 0 dan H = 0 (2.27)
U CV dT dan H C P dT (2.30)
Q C P dT (2.31)
U CV dT dan H C P dT (2.33)
dQ = 0
dV CV dV
CV dT RT 0 dT R
V T V
67
Jika CV tidak konstan (merupakan fungsi dari temperatur)
T2 V
CV dT 2
dV
R T V
T1 V1
Jika CV konstan
dT R dV
T CV V
T2 V
dT R 2 dV
T C V
T1 V V1 68
T2 V2
dT R dV
T C V
T1 V V1
R
ln T ln V V12
T2 V
T1
CV
R
lnT2 lnT1 lnV2 lnV1
CV
T2 R V2
ln ln
T1 CV V1
R
T2 V2 CV
ln ln
T1 V1 69
R CV
T2 V2
T1 V1
R CV
T2 V1 V1R CV
R CV
T1 V2 V2
70
Dengan cara yang sama bisa diperoleh:
R CP
T2 P2
T1 P1
CP CV
P2 V1
P1 V2
P1 V1CP CV
P2 V2CP CV
konstan (2.38)
71
Dengan definisi:
CP
CV
Maka :
R C P CV C P
1 1
CV CV CV
R C P CV CV 1 1 1
1 1
CP CP CP
72
Sehingga :
T V 1 konstan (2.39)
T P 1 konstan
(2.40)
P V konstan
(2.41)
73
T1 V1 1 T2 V2 1 1
Tawal Vawal 1
Takhir Vakhir
1 1
1
T1 P1 T2 P2 1 Tawal Pawal Takhir Pakhir
P1 V P2 V
1 2
Pawal Vawal
Pakhir Vakhir
74
Usaha dari suatu proses adiabatis dapat diperoleh dari
persamaan untuk Hukum I Termodinamika:
dU = dQ + dW
dW = dU = CV dT
W = CV T (2.42)
75
Bentuk alternatif untuk persamaan (2.42) dapat
diperoleh dengan mengingat bahwa:
C P CV R R R
1 CV
CV CV CV 1
Sehingga:
R T
W (2.43)
1
76
Karena RT1 = P1 V1 and RT2 = P2V2, maka:
Pers. (2.41):
P1 V1 P2 V2
V2 P1
V1 P2
1 1
V2 P1 P2
V1 P2 P1
78
1 1 1
P1V1 P2 P2
P1V1 P2
W 1 1
1 P1 P1 1 P1
1
P1V1 P2
W 1 (2.45)
1 P1
Atau:
1
RT1 P2
W 1 (2.46)
1 P1
79
PROSES POLITROPIS
Analog dengan proses adiabatis, proses politropis
didefinisikan sebagai proses yang memenuhi:
1
RT1 P2
W 1 (2.50)
1 P1
a
c
343K
1 1
V
84
PENYELESAIAN
343K CV = (3/2) R
423K
b
= (3/2) (8,314)
3 2 = 12,471 J mol-1 K-1
CP = (5/2) R
= (5/2) (8,314)
P a = 20,785 J mol-1 K-1
c
1 bar 343K
1
V CP 20,785
1,6667
CV 12,471 85
(a) Proses adiabatis (1 2)
Q=0
T1 P1 1 T2 P2 1
86
1 1
T1 P1 T2 P2
T P
1
1 1
1 T2 P2
1 1
1 1
T1 P1 T 2 P2
1 1 1,6667 0,6667
T T1 343
P2 1
1
P1 P1 1
T 2 T2 423
= 1,689 bar
87
(b) Proses isobaris (2 3)
88
(c) Proses isotermal (3 1)
Vakhir Pakhir
Q RT ln RT ln
H = U = 0 Vawal Pawal
P1 P3 P2
Q RT ln RT ln RT ln
P3 P1 P1
1,689
8,314 343,15 ln
1
= 1.495 J/mol
W Q 1495 J mol
89
Untuk keseluruhan proses:
U = 998 – 998 + 0 = 0
H = 1.663 – 1.663 + 0 = 0
90
TUGAS 1