FIRST LAW OF THERMODYNAMICS

Name: Mr. Burnett Date: 24/04/13 Class: 6B

First Law of thermodynamics

This is an application of the conservation of energy principle and states that: - the change in internal energy of a system (U) is equal to the heat supplied to or removed from it (Q) and the work done on or by it
Where, Q = heat supplied to or transferred from the system W = work done on or by the system U= change in internal energy of the system

U = Q - W

Sign Convention

Q is positive when heat is supplied to the system and negative when heat is transferred from the system W is positive if the external work is done by the system (gas expands) and it is negative if the work is done on the system (gas compressed). U is positive if the internal energy of the system increases.

E.g 1

2500J of heat is added to a system and 1800J of work is done on the system. What is the change in internal energy of the system? b) What would be the internal energy change if 2500J of heat is added to the system and 1800J of work is done by the system? Ans: a) U = 4300J; b) 700J

Tips to note

The internal energy increases by supplying heat to the system and/or by doing work on the system For an isolated system, one that does not transfer heat (Q =0J) and in which no work is done ( W = 0J) there is no change in internal energy U =0J. Internal energy is constant. Adiabatic processes are those that do not involve any transfer of heat (Q =0J). Thus U= -W. So for such processes the internal energy of the system is equal to the work

Work done by a gas

Consider a frictionless piston of surface area, A, as shown below,

In moving the piston outwards a distance x the gas does some work on the surroundings. The work done (W) here is equal to: W = F x; But the force, F, being exerted by the gas is equal to pressure (P) x Area (A), W = PA. x; But A .x = Volume (V); Thus

W = p V

E.g 1

A fixed mass of gas is cooled so that its volume decreases from 4.0 litres to 2.5 litres at a constant pressure of 1.0 x 105 Pa. Calculate the external work done on the gas. (1m3 = 1000 litres) Ans: -1.5 x 102 J

E.g. 2

A sample of gas is enclosed in a cylinder by a frictionless piston of area 60cm2. The cylinder is heated so that 400J of heat energy is supplied to the gas which then expands against atmospheric pressure and pushes the piston 20cm along the cylinder. Given that atmospheric pressure is 1.0 x 105Pa, calculate: a) the external work done by the gas (120J) b) the change in internal energy of the gas (280J)

Molar Heat Capacity

Oftentimes we dont know the mass of the gas but we know the number of moles there are in the gas. Definition: The amount of heat energy required to raise the temperature of 1mole of a substance by one kelvin (1K). There are two (2) forms of the heat formula with molar heat capacities: For heat transfer at constant pressure: Q = nCpT For heat transfer at constant volume: Q = nCvT Where Cp = Molar heat capacity at constant pressure Cv = Molar heat capacity at constant volume n = number of moles; Q = heat energy; T= temp change(K) Units: J/mol/ K or J mol-1 K-1

Cp vs Cv

The molar heat capacity at constant volume (Cv) is the heat energy required to produce a unit temperature rise in one mole of a gas when the volume is kept constant. The molar heat capacity at constant pressure (Cp) is the heat energy needed to produce a unit temperature rise in one mole of a gas when the pressure is kept constant.

Cp > Cv
Constant Pressure, Cp
Constant Volume, Cv

Heating a gas at constant pressure will cause an increase in its internal energy and work done by the gas itself.

Heating a gas at constant volume will only cause an increase in the internal energy of the gas. No work will be done by or on the gas.

Relation between Cp and Cv

Constant pressure (Cp) Q = U + W; W =pV Q= U + pV; Q = nCpT nCpT = nCvT + pV; pV = nRT where n = 1mol Cp = Cv + R; R= molar gas constant (8.31 J mol-1 K-1)

Constant volume (Cv) Q = U + W; W =pV but V = 0m3 Q = U = nCvT

Tips to Note

The addition or removal of heat does not have to change the temperature of a body (recall: latent heat Q = mL). Cp = Cv + R ; Cp > C v The values of Cp and Cv depend on the universal molar gas constant, R= 8.31 J mol-1 K-1 U = nCvT (always)

P-V graphs

Identify the lines drawn in p-V graphs above a) Isotherm ( represents an isothermal processconstant temperature) b) Isobar (represents an isobaric process constant pressure) c) Isochore ( represents an isochoric process constant volume)

Work done from p-V graphs

For isochoric or isovolumetric processes, there is no change in volume (V =0m3) so there is no work done, W= 0J.

Work done during a cycle

The shaded area on the graph represents the net work that is done on or by a gas during 1cycle. a- b: gas heated up no work done, W= 0J (constant volume) b-c: work done by the gas at constant pressure (W = p2 V) c-d: gas cools down at constant volume (W=0J) d-a: work done on gas at constant pressure. (W=p1V)

Net work done = Area shaded region = Area bcfe Area adfe Or Net work done = (p2 p1) x (V2 V1)

PQ

In which steps shown on the curve is work being done on the gas? a)A& B b)C&D Ans: b c) A&C d)B&D

Tips to note

You should be familiar with the areas of other figures such as the triangles and trapeziums in order to be competent on these questions.

1m3 = 1000Litres (L); always convert to S.I units unless told Work done in an isothermal process = W = nRT ln (nat log) (V2) otherwise ( V1) isobaric process = W = p V = p (V2 - V1)

isovolumetric/ isochoric process = W = 0J

E.g.- Work done in a cycle

Five moles of an ideal gas undergo a cycle consisting of two isobaric processes, ab and cd, and two isochoric processes, bc and da. Determine: a) The work done during the process ab b) The net work done during the entire cycle c) The temperature at a and b of the gas during the cycle d) The heat removed from the gas during the process c to d (hint: isobaric process) (take Cv for gas is = (5/2)R). (take 1atm = 1.01 x 105Pa or N/m2 R = 8.31 J mol-1K-1).

Solution
a) Given # of moles, n = 5. Now from a to b is an isobaric process (constant pressure), So the work done from a to b is: W = PV W = ( 5.0 x 1.01 x 105 )Pa x (6 2) x 10-3 m3 W = (5.05 X 105 )Pa x (4 x 10-3) m3 W = 2020J or 20.2 x 102 J = Work done over area abfe b) The net work during the entire cycle: W = (P2 - P1 ) x (V2 - V1) W = ( 5.05 1.01) x 105 x ( 4 x 10-3 m3) W = 16.16 x 102 J Or Net work done in a cycle = Work done for area abfe - Work done for area dcfe = 20.2 x 102 (1.01 x 105 )Pa x (4 x 10-3m3 ) = 16.16 x 102J c) For an ideal gas: pV = nRT; thus the temperatures at points a and b can be determined: Ta= paVa / nR = (5.05 x 105 Pa) x ( 2 x 10-3 m3) / 5 x (8.31) Ta = 24.3K

Solution cont
Tb = pbVb /nR Tb = (5.05 x 105Pa) x (6 x 10-3 m3) / 5 x (8.31) Tb = 72.9K
d) Cv = 5 R 2 Cp = 5 R + R = 7 R 2 2 the heat removed from the isobaric process c - d: Q = nCp T Q = 5 x (7 R) x ( 72.9 24.3) 2 Q = 5 x (7 x 8.31) x (48.6) 2 Q = 7067.7J

Work done in a cycle

Try these. Practice makes perfect ;) (y).

PQ2

The indicator diagram shows an energy cycle for 1mole of an ideal gas. The gas is cooled constant pressure (a to b), heated at constant volume (b to c) and then returned to its original state (c to a). Calculate: a) the gas temperature at a, b and c b) the heat removed from the gas during the process a to b. c) the heat supplied to the gas during the process b to c, and

d) the net work done in the cycle

(R = 8.31 J mol-1 K-1 ; Cv = (5/2)R c a

PQ- Net work done in a cycle

A fixed mass of gas is taken through the closed cycle ABCD as shown in the diagram. Calculate the work done by the gas during this cycle of events.

PQ2- Net work done in a cycle

The accompanying pressure-volume graph shows an engine cycle with one isothermal process, B-C. The working substance is an ideal gas. At point B, the pressure is 3.20x105 Pa and the volume is 0.0480 m3. At point C, the pressure is 2.10x105Pa and the volume is 0.0730 m3. At point A the volume is 0.0230 m3. What is, a) The gas temperature at A, B, C and D?

b) The net work done by the gas during one cycle?

c) The heat energy removed or supplied during the processes a to b, b to c and c to d? (R = 8.31 J/mol/K; Cp = 29 J mol-1 K-1 ).