1.

The first law

Chapter 2 2. Specific heat capacity
3. Application to processes
4. Examples

1. The first law

• nternal energy : .

( ) (Q ):

Notation (in the reference books):

Work: W / w, (A)
Heat: Q / q
 +

- U=Q+W

In the figure, the gas absorbs 400 J of heat and at the same
U: state function
time does 120 J of work on the piston. What is the change in
internal energy of the system?
U = Q1 + W1
= Q2 + W2 Wout =120 J
is positive: +400 J (Heat IN)
= Q3 + W3 is negative: - 120 J (Work OUT)


For a infinitesimal process 𝑑𝑈 = 𝛿𝑄 + 𝛿𝑊 Qin
400 J
Where:
“d” used for describing state function
“ ” used for describing path function
 Parameter Denotation Calculation
Q Q
Average heat =
capacity
C T1 −T 2 T

Q
Real heat capacity C dT
Constant-pressure  Q  H 
heat capacity
Cp   = 
 dT  p  T  p

Constant-volume  Q  U 
heat capacity
Cv   = 
 dT V  T V

Molar heat capacity of ideal gases:

Cp = C v + R
Cp = C v + R ?
1 mol ideal gas (T 1 ,P1,V1) 1 mol ideal gas (T1 +dT, P1, V1+dV)

1 mol ideal gas (T1 +dT, P 1 +dP, V1)

 – – –
Joule :
 – – ( )

: U=f(T).
→

• Effect of temperature: (Debye’s rule)

CP = a0 + a1.T + a2.T2
• CP = a0 + a1.T + a-2.T-2
or: CP = a0 + a1.T + a2.T2 + a-2.T-2

(ai : from Physicochemistry handbook)

 𝛿𝑊 = −𝑃 × 𝑑𝑉

 dU = Q − p.dV


V2
U = Q − V p.dV
1

a/ Isochoric (V = const or dV = 0) b. Isobaric (p = const or dp = 0)

V2
dV = 0 WP = −  p  dV = − P  V2 − V1 = − P  V
V2 V1

Wv = −  p  dV = 0 QP = U − W = U + P  V =  U + PV
V1 QP = H

𝑄 = Δ𝑈
Enthalpy is the sum of internal energy and the product of pV
 3. Application to processes 3. Application to processes

Ideal gas equation PV = nRT : Joule’s law: (for ideal gas)

Wp = -P V = - (PV) = - (nRT) = -nR T Internal energy of ideal gas just depends on temperature:
U = f(T)
 Up = Qp – nR T
or Up = H – nR T  U T = 0
V2
nRT V  P 
R: ideal gas constant, R = 1,987 cal/mol.K
QT = −WT = 
V1
V
 dV = nRT  ln  2  = nRT  ln  1 
 V1   P2 
= 8,314 J/mol.K
= 0,082 L.atm/mol.K

3. Application to processes 3. Application to processes

𝛿𝑞 + 𝛿𝑤 = du

𝐾= 𝑷 × 𝑽𝒏 = 𝒄𝒐𝒏𝒔𝒕
𝑑𝑢 = 𝑐 𝑑𝑇
𝑃 𝑣 𝑣 𝑃
→ 𝐾 − 1 𝑃𝑑𝑣 = 𝑐 𝑑𝑇 = =
𝑃×𝑣 = 𝑍×𝑅×𝑇 𝑃 𝑣 𝑣 𝑃

→ 𝑃𝑑𝑣 + 𝑣𝑑𝑃 = 𝑍𝑅𝑑𝑇

𝑐 − 𝑐 = 𝑍𝑅 𝑇 𝑣
=
𝑇 𝑣
𝑃𝑑𝑣 + 𝑣𝑑𝑃 = 𝑐 − 𝑐 𝑑𝑇

𝑇 𝑃
et: γ = (Adiabatic constant) =
𝑇 𝑃

− = 1−𝛾 𝐾+𝛾
𝑛 = 1−𝛾 𝐾+𝛾

→ − =𝑛

𝑷𝒗𝒏 = 𝒄𝒐𝒏𝒔𝒕
3. Application to processes

1 mol

T2= ?
0.2 mol diatomic ideal gas undergoes
a cycle starting at point A (2 atm, 1L).
Process from A to B is an expansion 0.2 mol diatomic ideal gas undergoes a cycle starting at
at constant pressure until the volume point A (2 atm, 1L). Process from A to B is an expansion
at constant pressure until the volume is 2.5 L, after which
is 2.5 L, after which is cooled at is cooled at constant volume until its pressure is 1 atm. It
constant volume until its pressure is 1 is then compressed at constant pressure until the volume
is again 1L, after which it is heated at constant volume
atm. It is then compressed at constant until it is back in its original state. Find (a) the work, heat
pressure until the volume is again 1L, and change of internal energy in each process (b) the
total work done on the gas and the total heat added to it
after which it is heated at constant during the cycle.
volume until it is back in its original
A system consisting of 0.32 mol of a monoatomic ideal gas
state. Find occupies a volume of 2.2 L, at a pressure of 2.4 atm.
The system is carried through a cycle consisting:
1. The gas is heated at constant pressure until its volume
(a) the work, heat and change of is 4.4L.
internal energy in each process 2. The gas is cooled at constant volume until the pressure
decreased to 1.2 atm
3. The gas undergoes an isothermal compression back to
(b) the total work done on the gas initial point.
(a) What is the temperature at points A, B and C
and the total heat added to it during (b) Find W, Q and ΔU for each process and for the entire
the cycle. cycle