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First Law of Thermodynamics

JU

Surrounding

U
w

System

dU
w q
= JU +
+
dt
dt dt

JU = rate of transfer due to matter exchange with surrounding

Three types of energy transfer: mass, heat, work

U=

For a mechanical system,

1 2
mv + mgh
2

First Law for a Closed System

In a closed system,

System
Surrounding

Into the system

U = w + q
The change of total internal
energy of a system
U is path-independent, w and q are path-dependent.
Molar internal energy,

Heat
It is energy in transfer due to temperature difference.
Amount of heat transfer = q. By convention, q > 0 if heat
transfers into the system.

Thermal equilibrium
(between system
and surrounding)

T = Tin - Tex = 0

Heat transfer can occur via two mechanisms:

o Conduction;
o Radiation;
o Convection is due to mass transfer, not a mechanism in thermodynamics.

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Rate of conduction
=

Fourier's law,

Rate of radiation between a and b

=

) StefanBoltzmann Law

where is the heat transfer rate, k is the thermal conductivity of

material, is the material emissivity (< 1 and = 1 for a black body),
is the Stefan-Boltzmann constant, A is system surface area, and T is
the absolute temperature (in Kelvin).

In classical thermodynamics, there is no way to calculate q

directly; it can be done indirectly, e.g., use 1st law.

Work

( )

The path is in 3-D space, is the direction of

the path.

or the tangent of

Types of work
Mechanical work: w = F x
Electrical work: w = F x = q E x = i E t
(since i = qv and v = x/t)
Other types of work include: surface tension work, elastic
deformation work, magnetic work, shaft work, etc.
By convention, w > 0 if external force does work on system.

Example: Find the work done by pex on the gas system.

x
pex

w = -pexAdx = -pexdV
(because dV < 0 and w > 0.)

For a volume with arbitrary shape, it can be shown

w = -pexdV
( )

(along a path)

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When the volume change is extremely slow and has no heat

dissipation, i.e., it is reversible, work is done through
equilibrium process. In this ideal situation, p is independent
of , and pex = p.
=

(along a path)

In classical thermodynamics, p pex, and work done by the

system is equal to -w.
-pdV is meaningless unless p is independent of .

Homework #1 has been posted.

Next Wed 8/26

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Example: Determine U, q and w of free expansion of ideal gas

at constant T from V1 to V2
U = 0 (for ideal gas, E is constant if T is constant)
w = pex V = 0

(real process)

q = U w = 0
wrev = pdV =

nRT
V
dV = nRT ln 2 < 0
V
V1

(reversible process)

qrev = U wrev = wrev > 0

State Variables
Physical quantities that characterize the system
at equilibrium and are independent of history.
Extensive: mass of a pure system (e.g., volume, energy)
Intensive: independent of mass (e.g., T, p)

U is a state variable.

Enthalpy
Define H = U + pV

(A state variable since U, p, and V are)

H can be considered as a generalized internal energy.

H is more useful than U in biology and chemistry studies,
where P is not changed. Thus, H can be determined by measuring total
heat transfer q at constant pressure.

For liquid and solid, U H if p is not >> 1 atm.

This is because their V/n (i.e., molar volume) and dV/V are small so that
PdV + Vdp << dU.

For ideal gas, U & H = 0 if T = 0.

Molar enthalpy,

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How to Determine Enthalpy of a

Pure Substance?
At p = 1 bar, T = 250C, standard state of a system
H is measured experimentally, and the data are listed in A.5 to A.7
Example: Determine enthalpy change of a chemical reaction at
standard state
+

Cp and CV
(dH)p = CpdT

if P = constant

(dU)V = CVdT

if V = constant

U
U
dE =
dV +
dT
V T
T V

U
CV =

T V

H
H
dH =
dT +
dP
T p
P T

H
Cp =

T p

i.e., they are

state variables

The derivation above assumes that there are no phase changes or

chemical reactions. Otherwise, the equations are invalid.

Why are CP and CV called heat capacity?

q = dU + pdV,
1. If P = constant,

q = dU + pdV = dH = CpdT
2. If V = constant,

q = dU + pdV = dU = CVdT
Heat is the amount of energy transferred into system to T.
In the past, it was thought to be the amount of an invisible fluid, known as
the caloric, flowing into the system to increase T.
This is a 2nd method to calculate q in classical thermodynamics.

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Molar heat capacity,

,

Specific heat capacity = heat capacity per unit mass.

For liquid and solid, the volume change is negligible. Thus,
dU dH and CV Cp
For ideal gas,

CP = CV + nR

How to Determine Heat Capacity of

a Pure Substance?
At p = 1 bar, T = 250C, standard state of a system
They are measured experimentally, and the data are
listed in specific handbooks.
With small T, they can be determined by
(dH)p = CpdT

if P = constant

(dU)V = CVdT

if V = constant

Heat capacity of ions is beyond the scope of this course.

Heat capacity of aqueous solution of ions is close to that of water.

6 ways to change U and H

Heating the system
Compression of the system
Phase change or transition (use data in Tables if it is at
standard state.) in heterogeneous systems
Mixing in heterogeneous systems
Transfer of chemicals between two different subsystems
in heterogeneous systems
Chemical reactions or composition change
Or the combination of these processes

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Phase
Broadly, each homogeneous part (no matter pure
or not) in a heterogeneous system is called a phase,
which is physically distinct, and mechanically
separable from the rest of the system.
Phase in this course refers to state of matter in textbooks of
introductory thermodynamics. For example, ice and vapor are two
different phases of water.

Phase transition (change): conversion from one phase to another,

occurring at the interface between two phases.

Phase Change
Examples:

boiling of water at 100oC and 1 atm

ice melting at

0oC

liquid gas

=>

and 1 atm

solid liquid

=>

Both processes require heat transfer into water (i.e., the system).
When a process involves phase change in the system, it
always occurs at interfaces of subsystems.

Phase 1

The interfaces do not have to be connected, such as vapor

bubbles in liquid water.
Phase 2

H of Phase Change

2 (

1)

For transition of moles of substance from phase 1 to

2 at fixed T and p,
,

,
,

( , )

( , )

1
,

(For pure system, molar H

is independent of n.)

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(heat transfer required for phase

change of moles of the substance)

For a pure system without phase change, an increase in T causes

changes in Hi,m
=

(i = 1 and 2)

This is the relationship of

at different temperature.

Temperature Dependence of Enthalpy

T2

H ( T2 ) = H ( T1 ) + C p dT
T1

(P = constant)

If both phase transition and T change are involved, H

needs to be added.
Tx

T2

T1

Tx

H (T2 ) = H (T1 ) + C pphase1dT + H (Tx ) + C pphase 2 dT

H(T2) is independent of the choice of Tx although D H depends
on both T and P.
The best way to calculate H(T2) is to choose Tx, at which H is
given.

Notes
1. Although phase transition can happen at any temperature, the direction of
spontaneous transition is temperature- and pressure-dependent.
For example, H2O(l) H2O(g). At p = 1 bar,
what is the direction of spontaneous transition at 25oC?
What is it at 150oC?
Can the direction be reversed?
2. The value of H for a material at certain T (e.g., 25oC and 100oC) and p
(e.g., 1 bar) can be found in thermodynamic tables.

3. When two phases are in equilibrium, T is called the phase transition

temperature (T ). For example, H2O(l) <=> H2O(g), T = 100oC if p = 1 bar
(i.e., the boiling point at 1 bar). And the phase change is reversible.

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http://www.youtube.com/watch?v=9q5gEZGoBnk
Video of boiling water in vacuum

Equilibrium Phase Transition of Water

pex

Example 1: Boiling 1 mole of water (18 g) at 1 atm and 100oC.

Heating
(H2O)liq

(H2O)steam

If q = 9.71 kilocalories, what are H and E after a

complete phase transition?

p
q

Solution:

q = H = 9.71 kcal
q = H = E + pV

U = q - pV

1 bar = 106 g/cm/sec2;

1 cm2g/sec2 = 2.39x10-8 cal

V = Vsteam - Vliq = RT/p - m/

= 30.6 L - 18x10-3 L 30.6 L = Vsteam
U = 9.71 kcal - 1. 0133x106 x 30.6x103 cm2 g/sec2
= 9.71 kcal 0.74 kcal = 8.97 kcal

Example 2: Heating of 1 mole of water (18 g) at 1 atm and 0oC.

(H2O)ice

heating
(H2O)liq

If q = 1.44 kcal, what is U?

Solution:

U = q - pV

H = q

V = Vliq - Vice = m(1/ liq - 1/ice)

= 18x10-3 L - 19.6x10-3 L = -1.6 x10-3 L

U = 1.44 kcal + 1. 0133x106 x 1.6 x10-3 x 103 cm2 g/sec2

= 1.44 kcal + 0.04 cal 1.44 kcal = q = H
Negligible due to small V change

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Standard State
Standard states of a pure system: p = 1 bar
Standard states of a non-pure system: p = 1 atm, and nk, pk, ck,
or xk (k = 1,2,,M) need to be specified.
Standard state can be at any T. Usually, standard state data
provided in Tables are either measured experimentally or
calculated at 250C or 298 K.
Note:

Standard state is a real state of pure systems, but can be a

hypothetical state of non-pure systems.

Standard Enthalpy of Chemical Reaction

At p = 1 bar and a constant T

r H 0 i H i0 (products) j H j0 (reactants)
where i = stoichiometric coefficient of ith substance, and the
system is at the standard state.
=
For pure subsystems within a system, Thus,
(i.e., molar enthalpy at 1 bar and the same T).

Example: Measurement of for ATP (adenosine 5triphosphate) hydrolysis in water at p = 1 bar.

ATPase

ATP + H2O

Thermometer

ATP

An insulated flask
and the solution is
well mixed.

A batch calorimeter

ADP + Pi
T2

H = C P dT = C P (T2 T1 )
T1

CP of solution in the flask = CP

of water
For pure liquid water at 1 atm,
CP = CV = mC* and C* = 4.18
kJ/kg/K

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Standard Enthalpy of Formation

Standard Enthalpy of Formation for a compound:
= enthalpy change for the formation of 1 mole of the
compound from elements in their most stable forms.
Stable element 1 + Stable element 2 + Compound

f H 0 H 0 (compound) j H j0 (elements in most stable form)

(pure compound)

(pure elements)

Assuming H j0 (elements in most stable form) = 0 at T = 25oC

At 1 bar and 25oC, standard
molar enthalpy enthalpy of
formation. It can be measured
experimentally.

H m0 (compound ) f H 0

The most stable state of an element

Example 1:

Gr Gr

C C

From Table A.5, at

25oC

or

Gr Dia

= 298 K

fH (Gr) = 0

Question 1: At 25oC, What are

H0(Gr) = 0
H0(Dia) = 1.895 kJ/mol

fH (Dia) = 1.895 kJ/mol

Cp,m(Gr) = 8.527 J/(K mol)
Cp,m(Dia) = 6.113 J/(K mol)

(Gr) and

Question 2: At 125oC = 398 K, what are

(Gr)?

398

H 0 (398) = H 0 (298) + C p0 (Gr ) dT = 0 + 852.7 J/mol

298

f H 0( 398 ) = f H 0( 298 ) +

( C )dT = 0 + 0 = 0

398

298

0
p

(trivial case)

0
0
0
or f H = H H (element reactants) = 852 .7 852 .7 = 0

Question 3: At 125oC = 398 K, what are H0(Dia) and fH(Dia)?

398

H 0 (398) = H 0 (298) + C p0 (Dia ) dT

298

= 1.895 kJ/mol + 611.3 K/mol = 2.506 kJ/mol

f H 0( 398 ) = f H 0( 298 ) +

( C )dT

398

298

0
p

= 1.895 kJ/mol + (611.3 852.7) K/mol = 1.654 kJ/mol

0
0
0
or f H = H H (element reactants)

= 2.506 kJ/mol 0.853 K/mol = 1.653 kJ/mol

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Example 4: For the reaction, C + O2 CO2, rH0 = -393.51

kJ/mol if C is graphite and rH0 = -395.41 kJ/mol if C is
diamond, what is fH0 or H0 of CO2?
Solution:

At p = 1 bar and T = 298K

H0(graphite) = 0
H0(diamond) 0
fH or H0 of CO2 = -393.51 kJ/mol

rH0 Depends on Temperature

1.

It can be calculated if there is no phase transition,

T2

r H 0 (T2 ) = r H 0 (T1 ) + r C P0 (T)dT

T1

where r C P0 =

0
P , mi

(products) C P0 ,mj (reactants)

Similarly,
T

f H 0 (T ) = f H 0 (298) + f C P0 dT
298

(Kirchhoffs law)

If there is a phase transition of a specific compound during the T change, H of that

compound needs to be considered. See HW 3.14 (Tinoco et al. 5th Ed.).

2. In many cases, rCP is unknown. Thus,

See the example of calorimetry.

are measured experimentally.

3. In biological system, T is small. It is often be assumed that

(T ).

(T )

Enthalpy of Chemical Reaction

At constant P and T (usually = P and T of mixture in reaction)

r H

H
= i H mi (products) j H mj (reactants )

where i = stoichiometric coefficient. Since Hi cannot be determined experimentally, it is

better to use

r H

H
= i f H i (products) j f H j (reactants )

Although

, it can be shown that two equations above are mathematically

equivalent to each other because of the mass conservation during reactions, i.e., both
equation give the same rH value.

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Summary

is unknown or cannot be measured experimentally. It is

calculated based on the following steps.

(298K) of compound is defined relative to

(298K) of elements;

(T) of compound/element is calculated, based

on its value at 298K;

(T) is calculated, based on

chemical;

(T) of the same

Standard Internal Energy of Chemical Reaction

Example: Determine molar internal energy of reaction rU for
the following reaction at 1 atm, 298oK, if rH = -589.56 kJ/mol.
4 HI (g) + O2 (g)

2 I2 (s) + 2 H2O (g)

Solution:

rU0 = rH - r(PV)
= rH - PrV
= rH - P[(V)H2O (V)HI (V)O2]
= rH - P[H2O HI O2]RT/P
= rH - rgRT = -589.56 (2-4-1)RT
= -589.56 + 7.43 = -582.13 kJ/mol

rE0 = rH0 (rg)RT0

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