Académique Documents
Professionnel Documents
Culture Documents
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
X
X = Xfinal - Xinitial
Varieties of Systems
Conservation of Energy
Isolated systems
Usys = 0
Open systems
Usys + Esurr = 0 Usys = - Esurr 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
Derive
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
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