Application of 1st law to closed systems

Heat
and/or

Heat- energy which crosses boundary of system by virtue of temperature difference

Quantity of heat which crosses boundary in process taking system form state 1 to state 2
is:
Q12 (J) q12 (J/kg) positive if heat flow is into system
Can be by conduction or radiation

Work – energy which crosses boundary of system by virtue of displacement under action
of force
Quantity of work which crosses boundary in process taking system form state 1 to state 2
is:
W12 (J) W12 (J/kg) positive if system does work on surroundings

Types of work
i) Acceleration of whole system by external force
2
W 12=−∫ F . ds
1

Negative because work done on system

F – applied force, ds – distance over which force is applied
But F=ma = m dv/dt
And V= ds/dt, ds=V.dt
2 2
dV V −V 1
Therefore W 12=−∫ m V . ds = W 12=−m ∫ V . dV =−m 2
1 dt 1 2
ii) Displacement of whole system

iii) Displacement of material within system by externally applied force

W always negative in this case

iv) Displacement of boundary system by action of pressure

s ds
Consider movement of piston from s to s+ds under action of pressure P. in limit as ds-0
dw=PA.ds =P.dv
A = area of piston

If expansion occurs sufficiently slowly for P to remain uniform within cylinder (reversible
2 2

expansion) thenW 12=∫ dw=∫ P . ds= area under P-V curve

1 1

v) Electrical work
Consider system to be length of wire with emf applied across its ends, causing
displacement of electrons internally (current)
Power = V.I = -dw/dt
2
W 12=−∫ VI .dt = -VI(t2-t1)
1

Can now express 1st law mathematically

For process taking system from state 1 to state 2
Net increase of total energy in system = net transfer of energy to system as heat & work
E2 – E1 = Q12 – W12
Or more generally
Q-W = ΔE =ΔU + Δ(mV2/2) +Δ(mgz)
If changes of KE and PE negligibly small then Q – W = ΔU
Equivalent relationships are q q – w = Δu
Or in differential form δQ – δW = ΔU, δq – δw = Δu

Note that in a cycle of processes, ΔU = 0 and so ∑Q - ∑W = 0