Chapter 6 Thermodynamics: The First Law

6-1 Systems, States, and Energy

What is Thermodynamics?
Thermodynamics
The study of the transformation of energy during chemical reaction and physical process
Heat of Reaction Steam Engine

Thermodynamics Laws
The 0th Law: Thermal Equilibrium

The 1st Law: Conservation of Energy The 2nd Law: Entropy

The 3rd law: Absolute Zero Temperature

 The First Laws

Conservation of Energy
Energy can be changed from one form to another, but it cannot be created or destroyed.

 X
X = Xfinal - Xinitial

System & Surroundings

Varieties of Systems

Definition of Internal Energy

Internal Energy UThe total energy of a system includes kinetics energy, intermolecular potential energy, bond energy, ionization energy .et al.

Conservation of Energy
Isolated systems
Usys = 0

Open systems
Usys + Esurr = 0 Usys = - Esurr Esurr

Usys

The First LawUsys

The First Law of Thermodyanmics Usys Esurr
Usys

Usys = q + w
q w

Heat q

Work w

Example
An automobile engine does 520 kJ of work and loses 220 kJ of energy as heat. What is the change in the internal energy of the engine? A chemical reaction known to release 1.78 kJ of heat take place in a constant-volume container. What are Usys , q and w?

What is work?
Expansion Work
The work of expansion against an external force

Nonexpansion work
The work does not involve a change in volume

Expansion Work
Work = force distance w = F l V = Pex A A = Pex V

Example
Suppose a gas expands by 0.5L against a pressure of 1.20 atm. How much work is done in the expansion? Suppose a gas expands by 0.5L against a pressure of 0.0 atm. How much work is done in the expansion? Energy Conversion Table
1 Pa*m3 = 1 kg/m/s2 * 1 m3 = 1 J 1 L*atm = 10-3 m3* 101325 Pa = 101.325 Pa*m3 =101.325 J

Reversible & Irreversible Expansion

Derive

wrev of Reversible Expansion

w = - PexdV , when P c ex
To calculate the work of reversible, isothermal expansion of an ideal gas from Vinitial to Vfinal constant temperature T.

Example
A piston confines 0.1 mol Ar in a volume of 1L at 25 . Two experiments are performed. In one, the piston is allowed to expand through 1L against a constant pressure of 1 atm. In the second, it is allowed to expand reversibly and isothermally to the same final volume. Which process does more work?

Heat

Heat ()
Heat
heat

Heat : q = CT
C Heat Capacity () Cs = Specific Heat Capacity = C/m, where m is the mass. Cm = Molar Heat Capacity = C/n, where n is the amount of moles.

Heat Capacities

Example
Potassium perchlorate, KClO4, is used as an oxidizer in fireworks. Calculate the heat required to raise the temperature of 10g KClO4 from 25 to an ignition temperature 900 . The specific heat capacity of KClO4 is 0.8111J/K/g.

Calorimeter :

Example
A chemical reaction known to release 1.78 kJ of heat take place in a constant-volume calorimeter containing 0.1L of solution and the temperature rose by 3.65. Next, 0.05L of 0.2M HCl and 0.05L of 0.2M NaOH were mixed in the same calorimeter and the temperature rose by 1.26 . What is the change in the internal energy of the meutralization reaction?

U
, U, U U PVT U UU

U
U = q + wexp + wnonexp , in gernal U = q + wnonexp , for a closed system U = wexp + wnonexp , for an adiabatic system U = 0, for an isolated system

wnonexp=0U
U = q + wexp = q Pex dV , where Pex C U = q + wexp = q Pex V , where Pex = C U = q, for a closed system where V = 0

U of the Ideal Gas System

Internal Energy U Monatomic Molecular Ideal Gas Linear Molecular Ideal Gas Nonlinear Molecular Ideal Gas

(3/2)RT = NA * 3 * (1/2kT) (5/2)RT = NA * 5 * (1/2kT) 3RT = NA * 6 * (1/2kT)

Boltzmanns constant k = R / NA = 1.381*10-23 J/K

How to Get U of Ideal Gases

Monatomic Molecular Ideal Gas

Linear Molecular Ideal Gas

Nonlinear Molecular Ideal Gas

State Function
95

60

25


Intensive Properties
PTd VnUn

Extensive Properties
VPEMU

Example
25 500cm3 1000cm3
U, qw 1Pa U, qw

First Law
U = q + w
U

q
q q

w
q w

Example
Suppose that 1 mol of ideal gas molecules at 292K and 3 atm expands from 8L to 20L and a final pressure of 1.2 atm by two different paths. Please calculate U, q and w for the two paths.
Path A is an isothermal, reversible expansion. Path B has two parts. In step 1, the gas is cooled at constant volume until its pressure has fallen to 1.2 atm. In step 2, it is heated and allowed to expand against a constant pressure of 1.2 atm until its volume is 20L and T=292K