Work and Heat

First Law of
Thermodynamics
Lesson 3.1 WORK & HEAT
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2 Content
 Internal Energy
 Work
 Heat
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3 First Law of Thermodynamic
 The First Law of Thermodynamics states that heat is a

form of energy, and thermodynamic processes are
therefore subject to the principle of conservation of
energy.
 This means that heat energy cannot be created or
destroyed. It can, however, be transferred from one
location to another and converted to and from other
forms of energy.
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4 INTERNAL ENERGY, ΔU
 We can test the validity of the first law by measuring only

the change in the internal energy of a system between
its initial state and its final state.
 The change in internal energy ΔU is given by:
ΔU = Uf – Ui
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5 COMPONENTS OF INTERNAL ENERGY
KINETIC ENERGY POTENTIAL ENERGY

 Consist of various types of  Is determined by the attractive
molecular motion and the interactions between electrons
movement of electrons within and nuclei and by repulsive
molecules. interactions between electrons
and between nuclei in individual
molecules, as well as by
interactions between molecules.
Change in energy can be determined experimentally.
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6 Example
S(s) + O2 SO2(g)
(we do not know the internal energy content of either the reactant molecules or the product molecules, but we
can measure the change in energy content, ΔU)
ΔU = U(product) – U (reactant)
= energy content of 1 mol SO2(g) – energy content of [1 mol S(s) + 1 mol O2(g)]
The reaction gives off heat (exothermic), the energy of the product is less than that of the
reactants, ΔU is negative
The sum of the energy changes must be zero (which means the total energy of the universe
does not change):
ΔUsys + Δusurr = 0
ΔUsys = -Δusurr
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7
WORK AND HEAT
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8
 Thus, if one system undergoes energy change ΔUsys, the rest of the universe, or
surroundings, must undergo a change in energy that is equal in magnitude but
opposite in sign (-ΔUsurr).
 A more useful form of the first law:
ΔU = q + w
(“sys” dropped)
 The change in the internal energy, ΔU, of a system is the sum of the heat
exchange q between the system and the surroundings and the work done w on
(or by) the system
 Note: q is positive for an endothermic process and negative for an exothermic
process; w is positive for work done on the system by the surrounding and
negative for work done by the system on the surroundings.
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9
 Internal energy is decreased when a system loses heat

to the surroundings or does work on the surroundings.
Thus, both q and w are negative.
 Internal energy is increased if heat is added to the

system or if work is done on the system. Thus, both q and
w are positive.
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10 WORK
 One way to illustrate mechanical work is to study the expansion and

compression of a gas (gas volume changes). Ex. The internal combustion
engine of the automobile.
Figure 1. A gas in a cylinder fitted with

weightless, frictionless movable piston at a
certain temperature, pressure, and
volume. As it expands, the gas pushes the
piston upward against a constant
opposing external atmospheric pressure,
Pext.
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11
Table 3.1 Sign Conventions for Work and Heat
Process Sign
Work done by the system on the surroundings -
Work done on the system by the surroundings +
Heat absorbed by the system from the surroundings (endothermic +

process)
Heat absorbed by the surroundings from the system (exothermic -
process)
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12
 The work done by the gas on the surroundings is

w = -PΔV
Where ΔV, the change in volume, is given by Vf-Vi.
Two conditions
 For gas expansion (work done by the system), ΔV > 0, so -PΔV is a negative
quantity.
 For gas compression (work done on the system), ΔV < 0, and –PΔV is a
positive quantity.
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13  Work can be defined as force (F) multiplied by distance (d)
w=Fxd
 The equation derive from the fact that pressure x volume can be expressed as
(force/area) x volume; that is
𝐹
PxV= x d3 = F x d = w
𝑑2
pressure volume
 Thus, the product of pressure and volume is equal to the force times distance, or
work.
 For a given increase in volume (that is, for a certain value of ΔV), the work done
depends on the magnitude of the external, opposing pressure Pext.
 If P is zero (that is, if the gas is expanding against a vacuum), the work done must
also be zero.
 If P is some positive, then the work done is given by –PΔV.
 The units for work done by or on a gas are liter atmospheres but should be express in
more familiar unit of joules.
1 L º atm = 101.3 J
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14 Sample problem 1
 A certain gas expands in volume from 2.0 L to 6.0 L at constant

temperature. Calculate the work done by the gas if it expands (a) against
the vacuum and (b) against a constant pressure of 1.2 atm.
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15 Solution to sample problem 1
 Strategy: The work done in gas expands is equal to the product of the external, opposing
pressure and the change in volume. What is the conversion factor between L .atm and J?
 A.) Because the external pressure is zero, no work is done in the expansion.
w = -PΔV
= -(0)(6.0-2.0) L
=0
 B.) the external opposing pressure is 1.2 atm, so
w= -PΔV
= -(1.2 atm) (6.0-2.0)L
=-4.8 L-atm
To convert the answer to joules, we write
W = -4.8 L.atm x 101.3J/1 L.atm
=-4.9x10^2J
 Check: Because this is gas expansion (work is done by the system on the surroundings), the
work done has a negative sign.
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16  Work is not a state function. We cannot write ΔW = wf –
wi for a change.
 Work done depends not only on the initial state and final
state, but also on how the process is carried out, that is
on the path.
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17 HEAT
 The other component of internal energy is heat, q.

 Like work, heat is not a state function.
 For example, it takes 4184 J of energy to raise the temperature of 100g of

water from 20oC to 30oC. The energy can be gained (a) directly as heat
energy from a Bunsen burner, without doing any work on the water; (b) by
doing work on the water without adding heat energy (ex, stirring the water
with magnetic stir bar); or (c) by some combination of the procedures
described in (a) and (b).
 It is important to note that regardless of which to note that regardless of
which the is taken, the change in internal energy of the system, ΔU,
depends on the sum of (q + w)
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18
 If changing the path from initial state to the final state increases so the
value of q, then it will decrease the value of w by the same amount and
vice versa, so that ΔU remains unchanged.
 SUMMARY: Heat and work are not state functions because they are not
properties of a system. They manifest themselves only during a process
(during a change). Thus, their values depend on the path of the process
and vary accordingly.
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19 Sample problem 2
 The work done when a gas is compressed in a cylinder like that

shown in figure 1 is 462 J. During this process, there is a heat transfer
of 128 J from the gas to the surroundings. Calculate the energy
change for this process.
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20 Solution
 Strategy: Compression is work done on the gas, so what is the sign for w?
Heat is released by the gas to the surroundings. Is this an endothermic or
exothermic process? What is the sign for q?
 Solution: to calculate the energy of the gas, we need equation, ΔU = q + w.
Work of compression is positive and because heat is released by the gas, q
is negative, therefore, we have
ΔU = q + w
= -128 J + 462 J
= 334 J
As a result, the energy of the gas increases by 334 J.
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21 WORKSHEET 4
 1. A gas expands from 264 mL to 971 mL at constant temperature. Calculate the

work done (in joules) by the gas if it expands (a) against a vacuum and (b) against
a constant pressure of 4.00 atm.
 2. A gas expands and does P-V work on the surroundings equal to 279 J. At the
same time, it absorbs 216 J of heat from the surroundings. What is the change in
energy of the system?
 3. Two ideal gases at the same temperature and pressure are placed in two equal
volume containers. One container has a fixed volume, while the other is a cylinder
fitted with a weightless movable piston like that shown in figure 1. Initially, the gas
pressure are equal to the external atmosphere pressure. The gases are then heated
with a Bunsen burner. What are the signs of q and w for the gases under these
conditions?
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22 References
 P. W. Atkins, J. de Paula. Physical Chemistry. Oxford University Press.

 R. Chang, and K. Goldsby. (2016) Chemistry, 12th Ed. McGraw-Hill, Inc., USA
 l. Levine. Physical Chemistry. McGraw-Hill Company.
 K. Laidler. Physical Chemistry. Houghton Mifflin Company.
 R. J. Silbey, R. A. Albertyand, M. G. Bawendi. Physical Chemistry. John Wiley.
 A. M. Halpern and J. H. Reeves. Experimental Physical Chemistry —A Laboratory
Textbook. Scott, Foresman and Co.
 D. P. Schoemaker, C. W. Garland and J.W. Nibler. Experiments in Physical
Chemistry. McGraw-Hill.
 F. A. Bettelheim. Experimental Physical Chemistry. W. B. Saundeers.
 R. J. Sime. Physical Chemistry: Methods, Techniques and Experiments. Saunders
College Publications.
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First Law of

 The First Law of Thermodynamics states that heat is a

 We can test the validity of the first law by measuring only

KINETIC ENERGY POTENTIAL ENERGY

Change in energy can be determined experimentally.

 Internal energy is decreased when a system loses heat

 Internal energy is increased if heat is added to the

 One way to illustrate mechanical work is to study the expansion and

Figure 1. A gas in a cylinder fitted with

Table 3.1 Sign Conventions for Work and Heat

Work done by the system on the surroundings -

Work done on the system by the surroundings +

Heat absorbed by the system from the surroundings (endothermic +

 The work done by the gas on the surroundings is

 A certain gas expands in volume from 2.0 L to 6.0 L at constant

 The other component of internal energy is heat, q.

 For example, it takes 4184 J of energy to raise the temperature of 100g of

 The work done when a gas is compressed in a cylinder like that

 1. A gas expands from 264 mL to 971 mL at constant temperature. Calculate the

 P. W. Atkins, J. de Paula. Physical Chemistry. Oxford University Press.

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