First Law of Thermodynamics

(a) The conservation of energy

First Law of thermodynamics

The internal energy of an isolated system is constant.

∆U = q + w (Mathematical statement of the First Law)
where w for the work done on a system, q for the energy
transferred as heat to a system.

(b) The formal statement of the First Law

The work needed to change an adiabatic system
from one specified state to another specified state
is the same however the work is done.

First Law of Thermodynamics

The formal statement of the First Law

The work needed to change

an adiabatic system
from one specified state
to another specified state
is the same
however the work is done.
2.3 Expansion Work

Work and heat

dU = dq + dw for infinitemal change
2.3 Expansion work
The work arising from a change in volume
(a) The general expression for work
dw = – F dz
dw = – Pex dV
Vf
w = − ∫ Pex dV
Vi

Various Works
 Constant Pressure Expansion

(b) Free expansion

w=0
(c) Expansion against constant pressure

Vf
w = − ∫ Pex dV
Vi
Vf
= − pex ∫ dV
Vi

= − pex (V f − Vi )
= − pex ∆V

Reversible Expansion

(d) Reversible expansion

A reversible change in thermodynamics
is a change that can be reversed by an
infinitesimal modification of a variable.
dw = -Pex dV = -P dV
Vf
w = − ∫ PdV
Vi

(e) Isothermal reversible expansion

Vf dV Vf
w = − nRT ∫ = − nRT ln
Vi V Vi
 Example 2.1

Calculate the work done when 50g of iron reacts with hydrochloric
acid in a (a) closed vessel of fixed volume, (b) an open beaker at 25 C.

(a) No volume change = no expansion work, 　 w = 0

(b) Gas drives back the atmosphere,

Expansion against constant atm. pressure w = PexV = Pex (Vf-Vi)

Fe(s) + 2HCl (aq) → FeCl2 (aq) + H2 (g)

nRT
w = − Pex ∆V ≈ − PexV f = − Pex × = −nRT
Pex

2.4 Heat Transactions

dU = dq + dwexp + dwe
dU = dq (at constant volume, no additional work)
dU = dqV

f
∆U = ∫ dq
i V
　∆U = qV for a measurable change
Calorimetry

* Calorimetry: Study of heat transfer during

physical and chemical processes

* Adiabatic bomb calorimeter

q = C ∆T
where C = calorimeter constant

* Calibration of calorimeter
q = I tV (charge electric potential)

J = CV (SI unit)

Heat Capacity

Heat capacity (C):

Ratio of heat supplied to the
temperature rise it causes

= Slope of the tangent to the T-U

curve at any temperature
Heat Capacity (Cv)

Cv: Heat capacity at constant volume

⎛ ∂U ⎞
CV = ⎜ ⎟
⎝ ∂T ⎠V
Molar heat capacity:
Heat capacity divided by
the amount of substance
Cm=C / n
Specific heat capacity:
Heat capacity divided by
the mass of substance
CS=C / m

Heat Capacity

Mono-atomic molecules Um = Um(0) + 3/2RT

Poly-atomic molecules Um = Um(0) + 3 RT
 Heat Capacity

⎛ ∂U ⎞
CV = ⎜ ⎟
⎝ ∂T ⎠V

* Internal energy change and temperature rise

dU = CV dT (at constant volume)
∆U = CV ∆T (at constant volume)
qV = CV ∆T

2.5 Enthalpy

(a) The definition of enthalpy:

Thermodynamic potential of the system
H = U + PV

dH = dq
(at constant pressure, no additional work)
∆H = qP
Justification

H = U +PV

dH = dU + d(PV) = dU + PdV + VdP

dH = dq – PexdV + PdV + VdP

if system P = Pex at equilibrium

dH = dq + VdP
at const P( dP = 0 )
∴ dH = dq at const P, no additional work.

U and H

f for a change at const. P

∆H = ∫ dq
i no additional work, only expansion
　H = qp work can occur.

f
∆u = ∫ dq for a change at const. V
i no additional work.
　U = qV
 Measurement
(b) The measurement of an enthalpy change

Differential Scanning Calorimeter

Adiabatic flame calorimeter (DSC)

Example 2.2
Illustration 2.4

The enthalpy of a perfect gas

H = U + PV = U + nRT
∆H = ∆U + ∆ngRT

Example 2.3
 Heat capacity at const. P

(c) The variation of enthalpy with temperature

⎛ ∂H ⎞
CP = ⎜ ⎟
⎝ ∂T ⎠ P
heat capacity at constant pressure CP
dH = CP dT (at constant pressure)
∆H = CP ∆T (at constant pressure)
qP = CP ∆T
c
C P ,m = a + bT + empirical expression
T2

Cv and Cp

for a change at const. Volume, no additional work.

⎛ ∂U ⎞
C =⎜ ⎟ ∆U = C V ∆ T ∆U = q V
⎝ ∂T ⎠V
V

qV = CV ∆ T

for a change at const. Pressure, no additional work

⎛ ∂H ⎞ ∆H = C P ∆ T ∆ H = qp
CP = ⎜ ⎟
⎝ ∂T ⎠P
qP = CP ∆ T
 Relation btw Cv and Cp

∆U = C V ∆ T ∆H = C P ∆ T
H = U + PV = U + nRT
∆H - ∆U = nR∆T = (CV - CP )∆ T

∴(CV - CP ) = nR

2.6 Adiabatic Changes

Perfect gas expands adiabatically:

can be treated as two-step changes

∆U = CV (Tf – Ti) = CV ∆T
∆U = q + w, but q=0 (adiabatic)
wad = CV ∆T
1/ c
⎛V ⎞
T f = Ti ⎜ i ⎟
⎜V ⎟
⎝ f ⎠
V f T fc = ViTi c where c = CV ,m / R
Reversible Adiabatic Expansion 1

∆U = CV ∆T → dU = CV dT
∆U = wad → dU = dwad = − PdV
∴ CV dT = − PdV
nRT C dT nRdV
CV dT = − dV → V =−
V T V
Tf f V
dT dV Tf Vf
CV ∫ = − nR ∫ → CV ln = −nR ln
Ti
T Vi
V Ti Vi
CV T f V
ln = ln i we can put c = CV / nR
nR Ti Vf
c c
⎛ Tf ⎞ V ⎛T ⎞ V
Therefore ln⎜⎜ ⎟⎟ = ln i → ⎜⎜ f ⎟⎟ = i → ViTi c = V f T f c
⎝ Ti ⎠ Vf ⎝ Ti ⎠ V f

Reversible Adiabatic Expansion 2

1/ c
T ⎛Vf ⎞
ViTi = V f T f → i = ⎜⎜ ⎟⎟
c c

T f ⎝ Vi ⎠
1 nR C P − CV C P
we know that = = = −1 ≡ γ −1
c CV CV CV
1/ c γ −1
PiVi T ⎛Vf ⎞ ⎛Vf ⎞
for perfect gas PV = nRT → = i = ⎜⎜ ⎟⎟ = ⎜⎜ ⎟⎟
Pf V f T f ⎝ Vi ⎠ ⎝ Vi ⎠
γ
P ⎛Vf ⎞
∴ i = ⎜⎜ ⎟⎟ → PV γ = Constant
Pf ⎝ Vi ⎠
 Reversible Adiabatic Expansion 3

PVγ = Constant for adiabatic change

PV = Constant for isothermal change

Reversible Adiabatic Expansion 4

For monoatomic perfect gas

3 5 5
CV ,m = R , C P ,m = R ∴ γ =
2 2 3

For non-linear polyatomic gas

4
CV ,m = 3R , C P ,m = 4 R ∴ γ =
3
PVγ = Constant
for reversible adiabatic change