Chapter 3

The second Law of Thermodynamics

1
 3.1- Motivation of the second Law

• Two equal blocks of copper are connected by a

wire. One block is at 20℃and the other at 30℃
(state A). The blocks are each at 25℃ (state B).

• A dilute gas at a temperature 𝑇occupies one half of

a vessel and the other half is vacuum (state A). When
the tap is open, the gas at the same temperature
𝑇 will occupy the whole of the vessel (state B).

2
• Question: Are the processes A  B and
B → A allowed?
• Answer: Energy is conserved for all A → B and
B → A processes. The processes are allowed by
the First Law.

• Question: Are the processes A → B and

B → A observed?
• Answer: Only the processes A → B are observed
to occur (spontaneously).

3
We observe many changes in our life to occur
spontaneously like:

 Cooling of a hot object.

 Expansion of a gas to fill any available volume.

What makes such processes spontaneous?

4
 Spontaneous changes
• Spontaneous change: a change that occurs without work
being done to bring it about, it has a natural tendencyto
occur.
• Non-spontaneous change: a change that can be brought
about only by doing work,it has no natural tendency to
occur.
• We expect that there exists a state function, 𝑆, that
characterizes the spontaneous direction of a process.

5
 3.2- Entropy
a- Direction of spontaneous change
Expansion of a gas
 Spontaneous to fill the volume, which means that matter tends
to become disordered (dispersed).
Cooling of a hot object
 Spontaneous to cool and heat transfer to surroundings, which
means that energy tends to become disordered.

 The apparent driving force of spontaneous changes is the

tendency of energy and matter to become disordered → the
measure of the disorder of matter and energy used in
thermodynamics is called the “Entropy, S”.
6
 x
The direction of spontaneous
change for a ball bouncing on a
floor. On each bounce some of its
energy is degraded into the thermal
motion of the atoms of the floor,
and that energy disperses. The
reverse has never been observed to
take place on a macroscopic scale.
we look for the direction of change that leads to dispersal of the total energy of the isolated
system.
The molecular interpretation of the
irreversibility expressed by the Second Law.
(a) A ball resting on a warm surface; the
atoms are undergoing thermal motion
(vibration, in this instance), as indicated by
the arrows. (b) For the ball to fly upwards,
some of the random vibrational motion
would have to change into coordinated,
directed motion. Such a conversion is highly
improbable.
7
x
b- Second law of thermodynamics

 “The entropy of an isolated system increases in the

course of a spontaneous change: ΔS tot > 0”.
Where S tot is the total entropy of the system and its surroundings.

 Or “The entropy of the universe tends to increase”.

Thermodynamically, irreversible processes (like cooling to

the temperature of the surroundings and the free expansion
of gases) are spontaneous processes, and hence must be
accompanied by an increase in total entropy.

8
 x
c- Thermodynamic definition of entropy
 As we have remarked, heat stimulates random motion in the
surroundings. On the other hand, work stimulates uniform motion
of atoms in the surroundings and so does not change their entropy.

 For any spontaneous process to occur, the energy is spread as

heat to the surroundings, therefore,
𝑑𝑞𝑟𝑒𝑣
𝑑𝑆 = ; where qrev is the heat supplied reversibly.
𝑇
𝑇2 𝑑𝑞𝑟𝑒𝑣
 And for a measurable change: ∆𝑆 = 𝑇1 𝑇
𝑞𝑟𝑒𝑣
 For an isothermal change (𝑇 constant): ∆𝑆 = (𝐽. 𝐾 −1 )
𝑇

9
 General considerations
1.Reversibility here is a thermal reversibility
example the equality of temperature on both sides,
therefore, smooth transfer of heat between system
and surroundings.
2.Energy is transferred as heat (𝑞) and not as work
𝑤 to make use of the disorderly motion of
molecules.
3.The presence of 𝑇 in the denominator takes into
account the disorder that is already present.
10
Example
Compare the entropy change when a 100 𝑘𝐽 of heat is
transferred to a large mass of water at 0℃ and 100℃.

At 273 K
𝑞𝑟𝑒𝑣 100000
∆𝑆 = = = + 366 𝐽𝐾 −1
𝑇 273
At 373 K
𝑞𝑟𝑒𝑣 100000
∆𝑆 = = = +268 𝐽𝐾 −1
𝑇 373

 Change in entropy is greater at lower 𝑇.

11
4.Entropy is an extensive property

To make it intensive → Divide by 𝑛, and get the

molar entropy, 𝑆𝑚 (J K-1 mol-1).

5.Entropy is a state function

A property that is path independent and its value

depends only on the present state of the system.

12
x

Sadi Carnot had proved that entropy is a state function

through the calculation of the integral:
𝑑𝑞𝑟𝑒𝑣
= 0 ; symbol denotes integration around a closed path
𝑇
This means that if entropy is a state function, then, the
overall change in entropy when making a cycle from the
initial state to the final
state and then back to the
initial state again is zero.
This is the basis of a Carnot cycle.

13
1. Reversible isothermal expansion from A to
B at Th; the entropy change is qh/Th, where
qh is the energy supplied to the system as
heat from the hot source.
2. Reversible adiabatic expansion from B to
C. No energy leaves the system as heat, so
the change in entropy is zero. In the course
of this expansion, the temperature falls
from Th to Tc, the temperature of the cold
sink.
3. Reversible isothermal compression from C
to D at Tc. Energy is released as heat to the
cold sink; the change in entropy of the
system is qc/Tc; in this expression qc is
negative.
4. Reversible adiabatic compression from D to
A. restores the system to its initial state. No
energy enters the system as heat, so the
change in entropy is zero. The temperature
rises from Tc to Th. 14
e- Calculating the entropy change for the isothermal
expansion of a perfect gas
For an isothermal expansion

∆𝑈 = 0 → ∆𝑈 = 𝑞 + 𝑤 = 0 → 𝑞 = −𝑤
Therefore, for a reversible change
𝑞𝑟𝑒𝑣
𝑞𝑟𝑒𝑣 = − 𝑤𝑟𝑒𝑣 → ∆𝑆 =
𝑇
𝑉𝑓
But 𝑞𝑟𝑒𝑣 = − 𝑤𝑟𝑒𝑣 = 𝑛𝑅𝑇𝐿𝑛 →
𝑉𝑖
𝑉𝑓
∆𝑆 = 𝑛𝑅𝐿𝑛
𝑉𝑖

15
Since entropy 𝑆 is a state function, the value of ∆𝑆
of the system is independent of path, and the above
equation holds for reversible and irreversible
changes.

𝑉𝑓
 When𝑉𝑓 > 𝑉𝑖 (expansion) → 𝐿𝑛 >0→
𝑉𝑖
∆𝑆 is positive.

𝑉𝑓
 When𝑉𝑓 < 𝑉𝑖 (compression) → 𝐿𝑛 <0
𝑉𝑖
→ ∆𝑆is negative.
16
Example 1
Calculate the entropy change when the volume occupied
by 1.00 mol of a perfect gas is doubled at constant
temperature.

Solution
𝑉𝑓 2
∆𝑆 = 𝑛𝑅𝐿𝑛 = 1.00 𝑥 8.314 𝑥 𝐿𝑛
𝑉𝑖 1
= + 5.76 𝐽𝐾 −1

17
Example 2

What is the change in entropy when the pressure of a

perfect gas is changed isothermally from 𝑃𝑖 to 𝑃𝑓 ?

Solution
𝑃𝑉 = 𝑛𝑅𝑇 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 → 𝑃𝑖𝑉𝑖 = 𝑃𝑓𝑉𝑓 →
𝑉𝑓 = 𝑃𝑖𝑉𝑖 /𝑃𝑓 →
∆𝑆 = 𝑛𝑅𝐿𝑛(𝑃𝑖𝑉𝑖/𝑃𝑓 𝑉𝑖) = 𝑛𝑅𝐿𝑛(𝑃𝑖/𝑃𝑓)

18
 x f- The change in entropy of the surroundings, 𝚫𝑺𝒔𝒖𝒓
Consider an infinitesimal transfer of heat 𝑑𝑞𝑠𝑢𝑟 to the surroundings.
The surroundings can be considered as a reservoir of constant volume
and constant pressure. Therefore,
𝑑𝑞𝑠𝑢𝑟 = 𝑑𝑈𝑠𝑢𝑟 or 𝑑𝑞𝑠𝑢𝑟 = 𝑑𝐻𝑠𝑢𝑟
Since internal energy is a state function, 𝑑𝑈𝑠𝑢𝑟 is independent of whether
the process is reversible or irreversible and the same applies to 𝑑𝑞𝑠𝑢𝑟 →
therefore

since𝑇𝑠𝑢𝑟 is constant what ever the change →

For instance, for any adiabatic change, qsur = 0, so For an adiabatic change: ΔSsur = 0
19
 Notes

1. The relation ∆𝑆𝑠𝑢𝑟 = ∆𝑞𝑠𝑢𝑟 / 𝑇𝑠𝑢𝑟

Can be used for any change that takes place
(reversible or irreversible).

2. For adiabatic change; ∆𝑞𝑠𝑢𝑟 = 0 → ∆𝑆𝑠𝑢𝑟 = 0

20
Example
Calculate the entropy change in the surroundings when
1.0 𝑚𝑜𝑙 of 𝐻2 𝑂(𝑙) is formed from its elements under
standard conditions at 298 𝐾, ∆𝐻𝑜 = − 286 𝑘𝐽 𝑚𝑜𝑙 −1 .

Solution
𝑞𝑠𝑢𝑟 = ∆𝐻𝑜 under constant pressure
∆𝑆𝑠𝑢𝑟 = 𝑞𝑠𝑢𝑟 / 𝑇𝑠𝑢𝑟 = 286 𝑥 103 𝐽 / 298 𝐾
−1
= + 960 𝐽 𝐾 .
Note: the amount of heat is released from the system
(reaction) to the surroundings (> 0)

21
 g- The Clausius inequality

It is known that more energy flows as work under

reversible conditions than under irreversible
conditions.
−𝑑𝑤𝑟𝑒𝑣 ≥ −𝑑𝑤 → 𝑑𝑤 − 𝑑𝑤𝑟𝑒𝑣 ≥ 0

Because internal energy is a state function, ∆𝑈 is

the same for reversible or irreversible paths between
the same two states;

22
𝑑𝑈 = 𝑑𝑞 + 𝑑𝑤 = 𝑑𝑞𝑟𝑒𝑣 + 𝑑𝑤𝑟𝑒𝑣 →
𝑑𝑞𝑟𝑒𝑣 − 𝑑𝑞 = 𝑑𝑤 − 𝑑𝑤𝑟𝑒𝑣 ≥ 0
Or 𝑑𝑞𝑟𝑒𝑣 ≥ 𝑑𝑞
Therefore, 𝑑𝑞𝑟𝑒𝑣 / 𝑇 ≥ 𝑑𝑞 / 𝑇
And since 𝑑𝑆 = 𝑑𝑞𝑟𝑒𝑣 / 𝑇 ≥ 𝑑𝑞 / 𝑇

𝑑𝑆 ≥ 𝑑𝑞 / 𝑇 Clausius inequality

23
Suppose that the system is isolated from its
surroundings (𝑑𝑞 = 0) →

According to Clausius inequality 𝑑𝑆 ≥ 0; this

means that “In an isolated system the entropy can
not decrease when a spontaneous change occurs”.

24
3.3 Entropy changes accompanying specific
processes
a- Expansion of a perfect gas
From the previous discussion, we know that for an
isothermal expansion of a perfect gas:
∆𝑆 = 𝑛𝑅 𝑙𝑛(𝑉𝑓/𝑉𝑖 )
The total change in entropy depends on how the
expansion takes place.
For any process;
𝑞𝑠𝑢𝑟 𝑞𝑟𝑒𝑣
𝑑𝑞𝑠𝑢𝑟 = − 𝑑𝑞𝑟𝑒𝑣 → ∆𝑆𝑠𝑢𝑟 = =−
𝑇 𝑇

∆𝑆𝑠𝑢𝑟 = − 𝑛𝑅 𝐿𝑛(𝑉𝑓/𝑉𝑖 )
25
For a reversible process
𝚫𝑺 = 𝒏𝑹𝑳n(𝑽𝒇/𝑽𝒊 )
𝚫𝑺𝒔𝒖𝒓 = − 𝒏𝑹𝑳n(𝑽𝒇/𝑽𝒊 )
Therefore;

𝚫𝑺 𝒕𝒐𝒕𝒂𝒍 = 𝚫𝑺 + 𝚫𝑺𝒔𝒖𝒓 = 𝟎

26
For irreversible isothermal free expansion;
𝑤 = 0 (free expansion) and
∆𝑈 = 0 (isothermal) → 𝑞 = 0 → ∆𝑆𝑠𝑢𝑟 = 0
therefore ; ∆𝑆 𝑡𝑜𝑡𝑎𝑙 = ∆𝑆 + ∆𝑆𝑠𝑢𝑟

∆𝑆 𝑡𝑜𝑡𝑎𝑙 = ∆𝑆 = 𝑛𝑅𝐿𝑛(𝑉𝑓/𝑉𝑖 ) > 0

As expected for an irreversible process.

27
Note: A reaction will be spontaneous if the total entropy
change is positive. It will not be spontaneous if the total
entropy change is negative.

A reaction would be exothermic with respect to the system

if it adds entropy to the surroundings and endothermic if it
reduces entropy of the surroundings. This means
∆𝑆𝑠𝑢𝑟𝑟 > 0 exothermic
∆𝑆𝑠𝑢𝑟𝑟 < 0 endothermic

28
 b- Heating
For an infinitesimal transfer of energy,𝑑𝑞
𝑻𝒇 𝑻𝒇
𝑑𝑆 = 𝑑𝑞𝑟𝑒𝑣 / 𝑇 𝑻𝒊
𝒅𝑺 = 𝑻𝒊
𝒅𝒒𝒓𝒆𝒗 /𝑻

𝑻𝒇 𝒅𝒒𝒓𝒆𝒗
∆𝑆 = 𝑺(𝑻𝒇 ) − 𝑺(𝑻𝒊) = 𝑻𝒊 𝑻

𝑻𝒇
Or 𝑺(𝑻𝒇 ) = 𝑺(𝑻𝒊) + 𝑻𝒊
𝒅𝒒𝒓𝒆𝒗 /𝑻

29
For a system at constant volume (with no non-expansion
work)
𝑑𝑞𝑟𝑒𝑣 = 𝐶𝑣 𝑑𝑇 𝑑𝑆 = 𝐶𝑣 𝑑𝑇/𝑇
and for a measurable change
𝑇𝑓
𝐶𝑣
∆𝑆 = 𝑑𝑇
𝑇𝑖 𝑇

30
And since 𝐶𝑣 can be considered constant for small
temperature ranges →
𝑇𝑓
𝑑𝑇
∆𝑆 = 𝐶𝑣
𝑇𝑖 𝑇

∆𝑆 = 𝐶𝑣 𝐿𝑛(𝑇𝑓/𝑇𝑖 )
Therefore 𝑆(𝑇𝑓 ) = 𝑆(𝑇𝑖 ) + 𝐶𝑣 𝐿𝑛(𝑇𝑓/𝑇𝑖 )

If heat transfer 𝑑𝑞 occurs at constant pressure

∆𝑆 = 𝐶𝑝 𝐿𝑛(𝑇𝑓/𝑇𝑖 )
Therefore
𝑆(𝑇𝑓 ) = 𝑆(𝑇𝑖 ) + 𝐶𝑝 𝐿𝑛(𝑇𝑓/𝑇𝑖 )
31
 Notes

 When 𝑇𝑓 > 𝑇𝑖 (Heating) → 𝐿𝑛(𝑇𝑓 /𝑇𝑖 ) > 0

∆𝑆 is positive (disorder increases).

 When 𝑇𝑓 < 𝑇𝑖 (Cooling) → 𝐿𝑛(𝑇𝑓 /𝑇𝑖 ) < 0

∆𝑆 is negative (disorder decreases).

32
Example
Calculate the change in molar entropy when
hydrogen gas is heated from 20°C to 30°C at
constant volume (𝐶𝑉,𝑚 = 22.44 𝐽𝐾 −1 𝑚𝑜𝑙−1 )

Solution
∆𝑆𝑚 = 𝐶𝑣, 𝑚 𝐿𝑛(𝑇𝑓/𝑇𝑖 )
= 22.44 𝐿𝑛(303.15/293.15)
= + 0.75 𝐽 𝐾 −1 𝑚𝑜𝑙−1 .

33
From the equation:
𝚫𝑺 = 𝑪𝒗 𝑳𝒏(𝑻𝒇/𝑻𝒊 )

𝚫𝑺 ↑ as 𝑪𝒗 ↑
Entropy change is directly
proportional to the heat capacity.

34
 c- Phase transition

In general for transitions at normal transition

temperatures:

∆𝑡𝑟𝑠𝑆 = 𝑞𝑝 / 𝑇𝑡𝑟𝑠

Or
∆ 𝑡𝑟𝑠𝑆 = ∆𝑡𝑟𝑠𝐻 /𝑇𝑡𝑟𝑠

35
 *Entropy of fusion, 𝚫𝒇𝒖𝒔𝑺

The entropy of fusion (∆𝑓𝑢𝑠𝑆) is the change of

entropy per mole of a substance at the melting
temperature 𝑇𝑓.

∆𝑓𝑢𝑠𝑆 = ∆𝑓𝑢𝑠𝐻 / 𝑇𝑓

Because ∆𝑓𝑢𝑠𝐻 > 0 → ∆𝑓𝑢𝑠𝑆 > 0 (𝑑𝑖𝑠𝑜𝑟𝑑𝑒𝑟 ↑)

36
Example
Calculate the entropy of fusion of ice at
0°𝐶(∆𝑓𝑢𝑠𝐻𝑜 = 6.01 𝑘𝐽𝑚𝑜𝑙−1 ).

Solution
∆𝑓𝑢𝑠𝑆 = ∆𝑓𝑢𝑠𝐻 / 𝑇𝑓 = 6010/273.15
= + 22 𝐽𝐾 −1 𝑚𝑜𝑙−1

37
 *Entropy of vaporization, 𝚫𝒗𝒂𝒑𝑺

The entropy of vaporization (∆𝑣𝑎𝑝𝑆), is the change

of entropy per mole of a substance at the boiling
temperature 𝑇𝑏.

∆𝑣𝑎𝑝𝑆 = ∆𝑣𝑎𝑝𝐻 / 𝑇𝑏

Because ∆𝑣𝑎𝑝𝐻 > 0 → ∆𝑣𝑎𝑝𝑆 > 0(𝑑𝑖𝑠𝑜𝑟𝑑𝑒𝑟 ↑)

38
Example
Calculate the entropy of vaporization of water at
100°𝐶 (∆𝑣𝑎𝑝𝐻𝑜 = 40.7 𝑘𝐽𝑚𝑜𝑙 −1 ).

Solution
∆𝑣𝑎𝑝𝑆 = ∆𝑣𝑎𝑝𝐻 / 𝑇𝑏
= 40700/373.15
= +109 𝐽𝐾 −1 𝑚𝑜𝑙−1

39
 *Trouton’s rule (empirical relation)
At the boiling point;
∆𝑣𝑎𝑝𝑆 = ∆𝑣𝑎𝑝𝐻 /𝑇𝑏 ≈ 85 𝐽𝐾 −1 𝑚𝑜𝑙−1
True for all liquids, except when H-bonding or
some other specific bonding is present.

Explain why
∆𝑣𝑎𝑝𝑆 𝐻2𝑂 = 109 𝐽𝐾 −1 𝑚𝑜𝑙−1 .
Solution
Because of the strong H-bonding in liquid water.
40
Example 1
Estimate ∆𝑣𝑎𝑝𝐻 of ethane from its boiling point
of −88.6°𝐶.

Solution
∆𝑣𝑎𝑝𝑆 = ∆𝑣𝑎𝑝𝐻 / 𝑇𝑏 ≈ 85 𝐽𝐾 −1 𝑚𝑜𝑙−1 →
∆𝑣𝑎𝑝𝐻 ≈ 85 𝑥 𝑇𝑏 ≈ 85 𝑥 184.55
≈ 16 𝑘𝐽𝑚𝑜𝑙−1

41
Example 2
Calculate the entropy change when argon at 25°𝐶
and 1.00 𝑏𝑎𝑟 in a container of 0.500 𝑑𝑚3 is
compressed to 0.0500 𝑑𝑚3 and cooled to −25°𝐶.
The heat capacity at constant volume of the argon
3
gas is 𝐶𝑣 , 𝑚 = 𝑅.
2

Solution
Because 𝑆 is a state function, we are free to
choose the most convenient path from the initial
state.
42
* Reversible isothermal compression
∆𝑆1 = 𝑛𝑅 𝐿𝑛(𝑉𝑓/𝑉𝑖 ) but 𝑛 is not known.
Since 𝑃𝑖 𝑉𝑖 = 𝑛 𝑅𝑇𝑖 → 𝑛 = 𝑃𝑖 𝑉𝑖 /𝑅𝑇𝑖 →
𝑃𝑖 𝑉𝑖
∆𝑆1 = ( 𝑅 𝐿𝑛(𝑉𝑓/𝑉𝑖 )
𝑅𝑇𝑖
= [𝑃𝑖 𝑉𝑖 / 𝑇𝑖] 𝐿𝑛(𝑉𝑓/𝑉𝑖 )
= 100.02 𝑥 103 𝑃𝑎 𝑥0.500𝑥10−3 𝑚3 / 298.15𝐾 𝑥
𝐿𝑛(0.0500/0.500)
= − 0.386 𝐽𝐾 −1

43
*Cooling at constant volume
∆𝑆2 = 𝐶𝑣 𝐿𝑛(𝑇𝑓/𝑇𝑖) = 𝑛 𝐶𝑣 , 𝑚 𝐿𝑛(𝑇𝑓/𝑇𝑖 )
= [𝑃𝑖 𝑉𝑖 / 𝑅𝑇𝑖 ]𝐶𝑣 , 𝑚 𝐿𝑛(𝑇𝑓/𝑇𝑖 )
∆𝑆2 = [100.02 𝑥 103 𝑃𝑎 𝑥 0.500 𝑥 10−3 𝑚3 𝑥 1.5
3
/ 298.15 𝐾] 𝐿𝑛(248.15/298.15)
2
= −0.0462 𝐽𝐾 −1

∆𝑆𝑡𝑜𝑡𝑎𝑙 = ∆𝑆1 + ∆𝑆2 = −0.386 – 0.0462

= −0.43 𝐽𝐾 −1

44
 d. The measurement of entropy
The entropy of a system at a temperature 𝑇 is
related to its entropy at 𝑇 = 0 𝐾 by measuring its
heat capacity 𝐶𝑝 at different temperatures and
evaluating the integral
𝑇𝑓 𝐶
𝑝
𝑆(𝑇𝑓 ) = 𝑆(𝑇𝑖) + 𝑑𝑇
𝑇𝑖 𝑇

Taking care to add the entropy of transition

(∆𝑡𝑟𝑠𝐻 / 𝑇𝑡𝑟𝑠) for each transition between 𝑇 = 0
and 𝑇.

45
If a substance melts at 𝑇𝑓 and boils at 𝑇𝑏, then the
entropy 𝑆(𝑇) above boiling point is:
𝑇𝑓
𝑆𝑚 (𝑇) = 𝑆𝑚 (0) + 𝐶𝑝,𝑚 (𝑠) 𝑑𝑇/𝑇 + ∆𝑓𝑢𝑠𝐻/𝑇𝑓
0
𝑇𝑏 𝑇
+ 𝐶𝑝,𝑚 (𝑙) 𝑑𝑇/𝑇 + ∆𝑣𝑎𝑝𝐻/𝑇𝑏 + 𝐶𝑝,𝑚 (𝑔)𝑑𝑇/𝑇
𝑇𝑓 𝑇𝑏

46
 3.4 Third Law of thermodynamics
At 𝑇 = 0, all energy of thermal motion has been quenched and in
perfect crystal all the atoms or ions are in a regular uniform array
𝑆 = 0 (ground state).

a- The Nernst heat theorem

The entropy change accompanying any physical or chemical
transformation approaches zero as the temperature approaches zero:
ΔS → 0 as T → 0 provided all the substances involved are perfectly
ordered.

47
 b- Third law of entropies
𝑆(0) = 0 called the third law of entropies.
The standard reaction entropy
∆𝑟 𝑆 𝑜 = 𝑜
𝜗𝑆𝑚 − 𝑜
𝜗𝑆𝑚
𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
Each term is weighted by the appropriate
stoichiometric coefficient (𝜗).
Standard reaction entropies are positive if there is
a net formation of gas in a reaction, and are
negative if there is a net consumption of gas.
48
49