1.

Introduction

As the weights fall, they give up potential energy and warm the water
accordingly. This was first demonstrated by James Joule, for whom the unit of
energy is named.
Schematic diagram for Joule´s experiment.
Insulating walls to prevent heat transfer
PHYSICAL CHEMISTRY 1 enclose water.
As the weights fall at constant speed, they
turn a paddle wheel, which does work on
water.
If friction in mechanism is negligible, the work
done by the paddle wheel on the water equal
the change of potential energy of the weights.

Ngo Thanh An
1

3. Heat and work

2. Internal energy

Internal energy involves energy on the microscopic scale Thermodynamic definition of work: It is a kind of interaction that would occur at the
system boundaries. It can be positive or negative.

For thermochemistry à the internal energy

is the sum of the kinetic energy of motion of
the molecules, and the potential energy
represented by the chemical bonds
between the atoms and any other
intermolecular forces that may be operative.
3. Heat and work 3. Heat and work

NHIEÄT COÂNG

3. Heat and work 4. Statement of first law

Sign convention

U=Q+W
4. Statement of first law 4. Statement of first law

U: state function
U = Q1 + W1
= Q2 + W2
= Q3 + W3

For a infinitesimal process

dU = dQ + dW
Where:
“d” used for describing state function
9
“ ” used for describing path function

4. Statement of first law 5. Heat capacity

In the figure, the gas absorbs 400 J of heat and at the

same time does 120 J of work on the piston. What is the
change in internal energy of the system?

DQ is positive: +400 J (Heat IN) Wby =120 J

DW is negative: -120 J (Work OUT)

DU = Q + W
Qin
= 400 J - 120 J 400 J
= +280 J Def. The specific heat capacity (c) of a substance is the amount of energy needed to
raise the temperature of 1kg of the substance by 1K (or 1 oC)
5. Heat capacity 5. Heat capacity

Q Q
Specific average heat capacity: C= =
T2 - T1 DT
dQ T2
Specific heat capacity:
C= Q = òT CdT
dT 1

For 01 mole of ideal gas: CP – CV = R

Effect of temperature on specific heat capacity:

CP = ao + a1T + a2T2
CP = ao + a1T + a-2T-2
CP = ai Ti (i = 0, 1, 2, –2)

5. Heat capacity 5. Heat capacity

• For ideal gas:

• Constant-
pressure
specific
• heats for some
gases

Cp = Cv + R
6. Application of first law 6. Application of first law

Isochoric process (V = const or dV = 0)

dW = - p ´ dV
dV = 0
V2

Þ dU = d Q - p.dV Wv = - ò p ´ dV = 0
V1

Þ
V2
DU = Q - òV p.dV QV = DU
1

17 18

6. Application of first law 6. Application of first law

Isobaric process (p = const or dp = 0) Isobaric process for ideal gas

Ideal gas equation

V2
pV = nRT :
WP = - ò p ´ dV = - P ´ (V2 - V1 ) = - P ´ DV Wp = p DV = D(pV) = D(nRT) =
Þ nRDT
V1
Up = Qp – nR T
QP = DU - W = DU + P ´ DV = D(U + PV )
QP = DH or Up = H – nR T

R: ideal gas constant, R = 1,987 cal/mol.K

= 8,314 J/mol.K
Enthalpy is the sum of internal energy and the product of pV 19 = 0,082 l.atm/mol.K 20
 6. Application of first law 6. Application of first law

Isothermal process for ideal gas Áp dụng nguyên lý 1: − = du (1)

Đặt tỷ lệ truyền năng lượng: = (2)
Với = (3)
Joule’s law: (for ideal gas) Ta sẽ có: −1 = (4)
Biết rằng phương trình khí thực: × = × × (5)
Internal energy of ideal gas just depends on Ta có: + = (6)
Ta cũng có: − = (7)
temperature: U = f(T). Thế phương trình (7) vào vế phải của phương trình (6), sẽ có:
+ = − (8)

Þ DU T = 0 Đặt hệ sốγ = . Đây chính là hệ số đoạn nhiệt.

Chia phươngtrình (8) cho phương trình (4), sẽ có:
V2 − = 1− + (9)
nRT æV ö æP ö
QT = -WT = ò
Nếu đặt giá trị = 1 − + (10)
´ dV = nRT ´ lnçç 2 ÷÷ = nRT ´ lnçç 1 ÷÷
V1
V è V1 ø è P2 ø
21
Ta sẽ có:
Hay là:
−
=
= (11)
(12)

6. Application of first law 6. Application of first law

× =

= =

=
7. Examples 7. Examples

A biatomic ideal gas undergoes a cycle starting at 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
cooled at constant volume until its pressure is 1 atm. It is
then compressed at constant pressure until the volume is
again 1L, after which it is heated at constant volume until
it is back in its original state. Find (a) the work, heat and
change of internal energy in each process (b) the total
work done on the gas and the total heat added to it during
the cycle.

A system consisting of 0.32 mol of a monoatomic ideal gas

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
is 4.4L.
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
initial point.
(a) What is the temperature at points A, B and C
(b) Find W, Q and ΔU for each process and for the entire
cycle

7. Examples 7. Examples
7. Examples 7. Examples

7. Examples 7. Examples