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PHYSICAL CHEMISTRYPROSES ADIABATIK
REVERSIBEL
Materi (4x pertemuan)
• Proses adiabatik reversibel• Hukum termodinamika 2
First Law
• dU, U = internal energy change of system
• dq, q = heat transfer into system• dw, w = work done on system
wqU
dwdqdU
Types of Work
• Volume Expansion
w = - Pext dV (P = pressure)• Stretching
w = - dl ( = tension)• Surface Expansion
w = - d ( = surface tension)
• Electricalw = dq ( = electrical potential)
Work
• Work is any interaction that could have as the sole effect the raising of a weight.
• Work = force x distance
dw = F dhw = F dh
• 1 kg
• 1 meter
Work of Expansion/Compression
pex = external pressureA = piston areadh = displacementdV = A dh = volume change for
the gasdw = F dh
Pex = F / A F = Pex A
dw = – Pex (A dh)
dw = – pex dV
gas
dh
pex
A
Reversible Changes
• A reversible change is one that can be reversed by an infinitesimal modification of a variable.
• In a reversible expansion or compression, pex = pgas
pex pgas
Irreversible Changes
• An irreversible change is one that is not reversible.
• In an irreversible expansion, pex < pgas
• In an irreversible compression, pex > pgas
pex pgas
pex pgas
Expansion Work at Constant P
VPdVPw
constP
dVPw
ex
V
V
ex
ex
V
V
ex
2
1
2
1
. le,irreversib if
Isothermal Reversible Work
1
2ln
/ gas, idealan if
,reversible if
2
1
2
1
V
VnRT
V
dVnRTw
VnRTp
pp
dVpw
V
V
gas
gasex
V
V
ex
Indicator Diagram: Compression
0
2
4
6
8
10
0 5 10 15 20
• pex
• Vi• Vf
• additional irreversible work
• reversible
work
Heat
• Heat is the energy transferred across a temperature difference.
• Temperature is the degree of “hotness” of an object.
q
Thigh
Tlow
Heat Capacity (C)
ifT TT
q
dT
qdC lim
0
• The heat capacity of a system is the ratio of the infinitesimal heat transfer dq to the accompanying infinitesimal temperature change dT. C depends on:· temperature· substance· path
Cv: Heat Capacity
2
1
,
,
T
T
mvV
mVV
V
V
TdCnq
TdCnqd
T
dqC
• Note: Heat absorbed at constant volume, qV = ∆U
Cp: Heat Capacity
2
1
,
,
T
T
mpp
mpp
p
p
TdCnq
TdCnqd
T
qC
• Note: Heat absorbed at constant pressure, qp = ∆H
q
Cp and Cv
RnCC
RCC
VP
mVmP
,,
HU PV CC • and • for solids and liquids
Common Paths
• Isochoric: V = constant (dV=0)
• Isobaric: p = constant (dp=0)
• Isothermal: T = constant (dT=0)
• Adiabatic: q = 0
Isothermal vs. Adiabatic
• An adiabatic process in one in which no heat is exchanged between the system and its surroundings.
• An isothermal process in one in which the initial and final temperatures are the same.
• Isothermal processes are not necessarily adiabatic.
Work
• Isochore: w = 0
• Isobar: w = -pV
• Reversible Isotherm: w = -nRT ln(Vf/Vi)
• Adiabat: w = U = nCv,m T
If CV is independent of
temperature between T1 and T2
State vs. Path Function• A state function is a
property of a system that depends only on its current state and not on how that state was reached.
• A path function depends on how the state was reached.
• state A
• state B
• path 1
• path 2
The First Law
• dU = dw + dq defines the internal energy change of a system.
• The internal energy is a function of state.
• Corollary: Energy is conserved in an isolated system.
• state A
• state B• w
• q
• w
• q
Energy Changes
• Because U is a function of state, U depends only on the initial and final states, and not the path followed between them.
if
U
U
UUdUUf
i
Changes in Internal EnergyFor a closed system at constant composition (n), the internal energy (U) of a system is a function of the volume (V) and temperature (T):
U(V, T)
When the volume changes infinitesimally from V to V+dV at constant temperature (T), the internal energy changes from its initial state (Ui) to its final state (Uf):
f i
T
UU U dV
V
Changes in Internal Energy
• If both the temperature and volume change infinitesimal amounts, dT and dV, the internal energy changes from its initial state (Ui) to its final
state (Uf):
f i
T V
U UU U dV dT
V T
Changes in Internal Energy
• Since the change in internal energy is infinitesimal, we can express the change between the initial and final states as the exact differential dU:
• The significance of this equation is that, in a closed system of constant composition (n), any infinitesimal change in the internal energy (U) is proportional to the infinitesimal changes of volume (V) and temperature (T)
T V
U UdU dV dT
V T
Changes in Internal Energy
• Recall that the heat capacity at constant volume, CV, is defined as:
• The heat capacity at constant volume, CV, is the slope of the internal energy (U) with respect to the temperature (T) and constant volume (V).
VV
UC
T
Changes in Internal Energy
• The internal pressure (πT) is the measure of the change in the internal energy of a substance as its volume is changed at constant temperature.
• Mathematically, the internal pressure (πT) is defined as:
TT
U
V
Changes in Internal Energy
• Because an infinitesimal change in the internal energy (dU) is related to a infinitesimal changes in volume (dV) and temperature (dT):
• Substituting:
• Gives:
TT
U
V
VV
UC
T
T V
U UdU dV dT
V T
T VdU dV C dT
Internal Pressure (πT)
• The internal pressure (πT) is a measure of the cohesive forces in the sample.
• Recall that:
• For a perfect gas, in which there are no interactions between the particles, the internal energy (U) is independent of the separation between the particles, and thus independent of the volume (V) of the sample.
• As a result, the internal energy (U) is independent of the volume (V) of the sample at constant temperature (T) .
• For an ideal gas:
T VdU dV C dT
0TT
U
V
Kkg
kJ Cp = Cv + R
For monatomic gases,
constants. are both and
R2
3R , C
2
5C vp
Enthalpy and Heat
• Enthalpy is defined: H = U + PV
• dH = dU + PdV + VdP
• at constant p,dH = dU + PdV = dqP – PdV + PdV
• dH = dqP or H = qP
Variation of H with T
TnCH
TdnCH
TdCnH
TdnCHd
mP
T
T
mP
T
T
mP
mP
,
,
,
,
2
1
2
1
pressure)constant (at
If Cp is independent of temperature between T1
and T2
Variation of H with T
12
21
222
1
2
2
2
11)(
/
)/(
;
/
2
1
2
1
2
1
2
1
TTncTTnbTnaH
TTdncTTdnbTdnaH
TdTcbTanH
then
TcbTaCTC
TdnCHd
T
T
T
T
T
T
T
T
pp
p
e.g. of function a is If
pressure)constant (at
Adiabatic Expansion
• dq = 0• dU = dw• for an ideal gas,
CVdT = – pexdV
• if reversible,pex = p = nRT/V
• therefore,CV(dT/T) = – nR(dV/V)
q
q
w
Reversible Adiabatic Expansion
i
f
i
fmV
mV
V
exV
V
VR
T
TC
V
dVR
T
dTC
dVV
nRTdTC
pdVdVpdTC
lnln,
,
Reversible Adiabatic Expansion
R
VTVT
V
V
T
T
V
VR
T
TC
ic
fc
f
iR
C
i
f
i
f
i
fmV
if
mV
/C c where
lnln
mV,
,
,
Reversible Adiabatic Expansion
iiff
ci
ci
cf
cf
i
c
iif
c
ff
ic
fc
VpVp
VpVp
VnR
VpV
nR
Vp
VTVTif
11
Polytropic Process Polytropic Process
PVn = C
Irreversible Adiabatic Expansion
ifexifV
exV
VVpTTC
dVpdTCdU
constant p assume ex
Adiabats vs. Isotherms
At any given pressure, Vadiabat < Visotherm because the gas cools during
reversible adiabatic expansion. In isothermal process when work is done, heat lost is replaced from the surrounding but in an adiabatic process it is not. In general which one has higher pressure for a given volume?
0
2
4
6
8
10
12
14
16
18
15 25 35 45 55 65
Volume
Pre
ss
ure
• Isotherm
• Adiabat
p
V
• Identify the nature of paths A, B, C, and D– Isobaric, isothermal, isovolumetric, and adiabatic
Lecture 27: Exercise 2Processes
p
V
AC
D
T1
T2
T3T4B
Equation of adiabatic process
1pV K
12TV K
13p T K
/p VC C K1 K2 K3 are constants
Calculation of adiabatic process
(1) The work of the adiabatic reversible process of ideal gas
2
1
dV
VW p V
2
1
= dV
V
KV
V ( )pV K
1 12 1
=1 1( )
(1 )K
V V
2 2 1 1=1
p V pVW
2 1( )1
nR T T
1 1 2 2p V p V K
Calculation of adiabatic process
(2) Work of adiabatic process
Cv(T2 –T1 )
because we do not introduce any other limitation conditions, this formula can be applied in adiabatic process of closed system which has fixed composing, need not always ideal gas, or reversible process.
W = U =