Lecture 16

Monday, October 13, 2014

13:07

Heat, Work, & Internal Energy

First law of thermodynamics CH2 V an Holde

Internal Energy and First Law of Thermodynamics

Thermodynamic system:
All materials that are under study
Surroundings - the rest of the universe
Open system can exchange matter with surroundings
Closed ( isolated) system cannot exchange matter or energy

Boundary between system and surrounding in contact.

Adiabatic - no change in temperature
Diathermal - T1n = T2n and P1n = P2n
Internal energy forms:
Kinetic energy of molecules
Potential energy
Internal energy of molecular vibrations and rotations
Internal energy stored in the form of chemical bonds
1st Law of Thermodynamics
Internal energy of isolated system is constant
Energy cannot be created or destroyed
U of the system = U of surroundings
U total = U system + U surroundings = 0
Thermodynamic system, no chemical reactions
U = q + w
where U is the change of internal energy, q is heat, and w is work
Work quantity of energy that flows across the boundary that can be used position o
mass in surroundings
Sign convention:

h2 < h1 Height is lowered Work done by surroundings on system is positiv

of

ve

U = q + w
where U is the change of internal energy, q is heat, and w is work
Work quantity of energy that flows across the boundary that can be used position o
mass in surroundings
Sign convention:

h2 < h1 Height is lowered Work done by surroundings on system is positiv

W > 0

U > 0

Height is raised

Work done by system on surroundings is posi

W < 0

U < 0

How to calculate work

F= Fdl
F is force, l is change of distance
P = F/A
P is pressure, A is area
F = P_extdAdl = P_extdV
P_ext is external pressure
dV = dA dL
W = P_ext dV
Example: Calculate work involved in expanding of 20.0 L of ideal gas to a final volum
85.0 L against constant external pressure 2.50 bar

Work

1 bar = 10^5 Pa 1L = 10^-3 m^3

W = P_ext dV
= P_ext dV
= P_ext V
= (2.50 bar (10^5 Pa/1bar)) ((85.0L 20.0L)(10^-3 m^3/1L))
= 16250 kJ

Work appears during change of state (transient)

Work change internal energy of system
Types of work:
Volume expansion W = P_ext dV
Stretching

W = dL
is tension

Surface expansion W = d

is surface tension
is area
Electrical work

W = dq
is potential
q is charge

Example: a water bubble is expanded from radius 1.00 cm to 3.25 cm. The surafce

of

ve

itive

me of

 is area
Electrical work

W = dq
is potential
q is charge

Example: a water bubble is expanded from radius 1.00 cm to 3.25 cm. The surafce
tension of water is = 71.99 N/m. How much work was done?
W = d
surface of sphere = 4r^2
W = 2 (_f _i)

* multiplied by 2 to account for

inner and outer surface of the
bubble

= 2 4 ( r_f^2 r_i^2)
= 8 71.99 N/m ( 3.25 cm^2 1.00 cm^2) (10^-4 m^2/ 1 cm^2)
= 1.73 J

Heat
Heat Capacity
State Functions, Path Functions
Equilibrium Change and Reversibility