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2.

1 Discuss the statement that a system and its surroundings are distinguished by specifying
the properties of the boundary that separates them.
A system is the part of the world in which we have a special interest. The surroundings are
where we make our observations.
The surroundings remain at constant temperature regardless of how much energy flows
into or out of them. They are so huge that they also have either constant volume or
constant pressure regardless of any changes that take place to the system. Thus, even
though the system might expand, the surroundings remain the same size.
There are three types of systems:
- Open system: it can exchange both energy and matter with its surroundings.
- Closed system: it can exchange energy but not matter with its surroundings.
- Isolated system can exchange neither matter nor energy with its surroundings.

Open: Closed: Isolated

2.2 What is (a) temperature, (b) heat, (c) energy?


Heat (q): is energy in transit as a result of a temperature difference.
Temperature (T): is an intensive property that is used to define the state of a system and
determines the direction in which energy flows as heat.
Energy: is the capacity to do work, and work is done to achieve motion against an
opposing force.

2.3 Provide molecular interpretations for work and heat.


The temperature is the single parameter that tells us the relative populations of the
available energy levels in a system.
Molecules can possess only certain energies (energy is ‘quantized’). At any given
temperature, the numbers of molecules that occupy the available energy levels depend on
the temperature: at low temperatures, most molecules are in the lowest energy states. As
the temperature is raised, more molecules occupy states of higher energy, so the
population spreads into these upper states.

When a weight is raised, all its atoms move in the same direction. This observation
suggests that work is the mode of transfer of energy that achieves or utilizes uniform
motion in the surroundings.

Now consider the molecular nature of heat. When energy is transferred as heat to the
surroundings, the atoms and molecules oscillate more vigorously around their positions or
move more rapidly from place to place. The key point is that the motion stimulated by the
arrival of energy from the system as heat is disorderly, not uniform as in the case of doing
work. This observation suggests that heat is the mode of transfer of energy that achieves
or utilizes disorderly motion in the surroundings.

2.4 Are the law of conservation of energy in dynamics and the First Law of thermodynamics
identical?
Law of conservation of energy: It is the principle of thermodynamics and states that the
total amount of energy in any isolated system remains unchanged over time, although this
energy can be transformed into another form of energy.
It is one of the fundamental laws of physics and its theory is about energy is not created or
destroyed, it is only transformed. This implies that mass under certain conditions can be
considered as a form of energy.
Law of conservation of energy. It is the principle of thermodynamics and states that the
total amount of energy in any isolated system remains unchanged over time, although this
energy can be transformed into another form of energy.
It is one of the fundamental laws of physics and its theory is about energy is not created or
destroyed, it is only transformed. This implies that mass under certain conditions can be
considered as a form of energy.

On the other hand, we know that energy is neither created nor destroyed, it only
transforms. It is the general principle of conservation of energy. Well, the first law of
thermodynamics is the application to thermal processes of this principle. This assumes
that the internal energy in an isolated system is constant.

First law of thermodynamics:


∆U = ∆Q + ∆W [J]

2.5 Explain the difference between expansion work against constant pressure and work of
reversible expansion and their consequences.
Expansion work against constant pressure:
Because many chemical reactions produce gas, one very important type of work in
chemistry is expansion work, the work done when a system expands against an opposing
pressure.

When a system expands through a volume ΔV against a constant external pressure pex the
work done is:
w = -Pex x ∆V

Gas Gas

V1 V2
Pext = cte

Reversible expansion:
Because the external pressure is infinitesimally less than the pressure of the gas at some
stage of the expansion, the piston moves out. However, suppose we increase the external
pressure so that it became infinitesimally greater than the pressure of the gas; now the
piston moves in. That is, when a system is in a state of mechanical equilibrium, an
infinitesimal change in the pressure results in opposite directions of motion. A process
that can be reversed by an infinitesimal change in a variable—in this case, the pressure —
is said to be reversible.

• A system does maximum expansion work when the external pressure is equal to that of
the system at every stage of the expansion (pex = p).
• A system does maximum expansion work when it is in mechanical equilibrium with its
surroundings at every stage of the expansion.
• Maximum expansion work is achieved in a reversible change.

We cannot write down the expression for maximum expansion work simply by replacing
pex in
w = -Pex x ∆V, by p (the pressure of the gas in the cylinder) because, as the piston moves
out, the pressure inside the system falls.
To make sure the entire process occurs reversibly, we have to adjust the external pressure
to match the changing internal pressure.

w = -nRT x ln(Vf/Vi)

2.6 Explain the difference between the change in internal energy and the change in enthalpy
of a chemical or physical process.
Internal energy: the internal energy, U, of the system, is the sum of all the kinetic and
potential contributions to the energy of all the atoms, ions, and molecules in the system.
The internal energy is the grand total energy of the system. It has a value that depends on
the temperature and, in general, the pressure. The internal energy is an extensive property
because 2 kg of iron at a given temperature and pressure, for instance, has twice the
internal energy of 1 kg of iron under the same conditions.

The fact that U is a state function implies that a change, ΔU, in the internal energy between
two states of a system is independent of the path between them. If we compress a sample
of gas until it reaches a certain pressure and then cool it to a certain temperature, the
change in internal energy has a particular value. If, on the other hand, we change the
temperature and then the pressure, but ensure that the two final values are the same as in
the first experiment, then the overall change in internal energy is exactly the same as
before.

Enthalpy: is equal to the system's internal energy plus the product of its pressure and
volume. When a process occurs at constant pressure, the heat evolved (either released or
absorbed) is equal to the change in enthalpy. Enthalpy (H) is the sum of the internal
energy (U) and the product of pressure and volume (PV).
*

2.7 Specify and explain the limitations of the following expressions:


(a) q = nRT ln(Vf/Vi)
For the isothermal, reversible expansion of a perfect gas
• When Vf > Vi, as in an expansion, the logarithm is positive and we conclude that q > 0, as
expected: flows as heat into the system to make up for the energy lost as work.
• The greater the ratio of the final and initial volumes, the greater the influx of energy as
heat.
• The higher the temperature, the greater the quantity of heat that must enter for a given
change in volume: we have seen that more work is done at a higher temperature, so more
heat must enter to make up for the energy lost.
(b) ∆H = ∆U + p∆V
If change is with a constant pressure

(c) Cpm –Cvm = R


For a perfect gas:
It shows that the molar heat capacity of a perfect gas is greater at constant pressure than
at constant volume. This difference is what we should expect. At constant volume, all the
energy supplied as heat to the system remains inside and the temperature rises
accordingly. At constant pressure, though, some of the energy supplied as heat escapes
back into the surroundings when the system expands and does work.
As less energy remains in the system, the temperature does not rise as much, which
corresponds to a greater heat capacity.
3.1 Define the terms (a) standard enthalpy of vaporization, (b) standard enthalpy of fusion;
(c) standard enthalpy of sublimation; (d) standard enthalpy of ionization; (e) standard
electron-gain enthalpy; (f) mean bond enthalpy, and identify an application for each one.
(a) The energy that must be supplied as heat at constant pressure per mole of molecules
that are vaporized under standard conditions (that is, pure liquid at 1 bar changing to
pure vapour at 1 bar) is called the standard enthalpy of vaporization of the liquid, and is
denoted Δvap H.
For example, 44 kJ of heat is required to vaporize 1 mol H2O (l) at 1 bar and 25°C, so
ΔvapH = 44 kJ mol-1. All enthalpies of vaporization are positive, so the sign is not
normally given.
(b) Another common phase transition is fusion, or melting, as when ice melts to water or
iron becomes molten. The change in molar enthalpy that accompanies fusion under
standard conditions (pure solid at 1 bar changing to pure liquid at 1 bar) is called the
standard enthalpy of fusion, ΔfusH.
Its value for water at 0°C is 6.01 kJ mol-1 (all enthalpies of fusion are positive, and the sign
need not be given), which signifies that 6.01 kJ of energy is needed to melt 1 mol H2O(s) at
0°C and 1 bar.
(c) The direct conversion of a solid to a vapour is called sublimation. The reverse process
is called vapour deposition. Sublimation can be observed on a cold, frosty morning, when
frost vanishes as vapour without first melting. The frost itself forms by vapour deposition
from cold, damp air. The vaporization of solid carbon dioxide (‘dry ice’) is another
example of sublimation. The standard molar enthalpy change accompanying sublimation
is called the standard enthalpy of sublimation, ΔsubH.
(d) With individual atoms and molecules. Among the most important is the standard
enthalpy of ionization, ∆ionH, the standard molar enthalpy change accompanying the
removal of an electron from a gas-phase atom (or ion). For example, because the standard
enthalpy of ionization of hydrogen atoms is reported as 1312 kJ mol. This value signifies
that 1312 kJ of energy must be supplied as heat to ionize 1 mol H(g) at 1 bar (and 298.15
K).

(e) The reverse of ionization is electron gain, and the corresponding molar enthalpy
change under standard conditions is called the standard electron gain enthalpy, ΔegH. This
quantity is closely related to the electron affinity. For example, because experiments show
that it follows that the electron gain enthalpy of Cl atoms is −349 kJ mol-1.

(f) The final atomic and molecular process to consider at this stage is the dissociation, or
breaking, of a chemical bond, as in the process

The corresponding standard molar enthalpy change is called the bond enthalpy. Mean
bond enthalpies, ΔHB, which are the averages of bond enthalpies over a related series of
compounds. For example, the mean HO bond enthalpy, ΔHB(H—O) = 463 kJ mol-1, is the
mean of the O —H bond enthalpies in H2O and several other similar compounds, including
methanol, CH3OH.

3.2 Define the terms (a) standard reaction enthalpy; (b) standard enthalpy of combustion;
(c) standard enthalpy of formation, and identify an application for each one.
(a) The standard reaction enthalpy (the ‘standard enthalpy of reaction’), ΔrH , is the value
of the reaction enthalpy when all the reactants and products are in their standard states:

The standard reaction enthalpy is the change in enthalpy of the system when the reactants
in their standard states (pure, 1 bar) are completely converted into products in their
standard states (pure, 1 bar), with the change expressed in kilojoules per mole of reaction
as written. Thus, if for the reaction 2 H2(g) + O2(g) → 2 H2O(l) we report that
ΔrH = −572 kJ mol-1, then the ‘per mole’ means that the reaction releases 572 kJ of heat
per mole of O2 consumed or per 2 mol H2O formed.

(b) One commonly encountered reaction is combustion, the complete reaction of a


compound, most commonly an organic compound, with oxygen, as in the combustion of
methane in a natural gas flame:

By convention, combustion of an organic compound results in the formation of carbon


dioxide gas, liquid water, and—if the compound contains nitrogen— nitrogen gas. The
standard enthalpy of combustion, ΔcH , is the change in standard enthalpy per mole of
combustible substance. In this example, we would write Δ c H (CH4, g) = −890 kJ mol-1.

(e) The standard enthalpy of formation, ΔfH , of a substance is the standard enthalpy
(per mole of the substance) for its formation from its elements in their reference states.
The reference state of an element is its most stable form under the prevailing condition.
For example, the standard enthalpy of formation of liquid water (at 25°C, as always in this
text) is obtained from the thermochemical equation

3.3 A primitive air-conditioning unit for use in places where electrical power is not available
can be made by hanging up strips of linen soaked in water. Explain why this strategy is
effective.
Water evaporates and absorbs energy. During evaporation a molecule of water absorbs
latent heat. Then, you know that the air around these strips will cool down.

3.4 Describe at least two calculational methods by which standard reaction enthalpies may
be predicted. Discuss the advantages and disadvantages of each method.
The first method is from the training energy.

The second method is Hess Law.


The standard enthalpy of a reaction is the sum of the standard enthalpies of the reactions
into which the overall reaction may be divided.

The first method is easier but we need enthalpies of formation of products and reactants.

3.5 Why is it important to distinguish between the standard state and the reference state of
an element?
The reference state of an element is its most stable form under the prevailing conditions.
Don’t confuse ‘reference state’ with ‘standard state’: the reference state of carbon at 25°C
is graphite; the standard state of carbon is any specified phase of the element at 1 bar.

3.6 Discuss the limitations of the expressions:


(a) ∆𝒓𝑯 = ∆𝒓𝑼 + ∆𝒗𝒈𝒂𝒔 𝑹𝑻
The molar volume of a gas, and therefore the value of pVm, is about 1000 times greater
and cannot be ignored. For gases treated as perfect, pVm may be replaced by RT.
Therefore, if in the chemical equation the difference (products – reactants) in the
stoichiometric coeAcients of gas phase species is Δvgas.
(b) ∆𝒓𝑯𝒐 (𝑻′ ) = ∆𝒓𝑯𝒐 (𝑻) + ∆𝒓𝑪𝒑𝒐 · (𝑻′ − 𝑻)
Kirchhoff’s law. We see that, just as we anticipated, the standard reaction enthalpy at one
temperature can be calculated from the standard reaction enthalpy at another
temperature provided we know the standard molar constant-pressure heat capacities of
all the substances. These values are given in the Data section. The derivation of Kirchhoff ’s
law supposes that the heat capacities are constant over the range of temperature of
interest, so the law is best restricted to small temperature differences (of no more than
100 K or so).

3.7 In the earlier literature, and still not uncommonly, you will find the expressions ‘heat of
combustion’ and ‘latent heat of vaporization’. Why are the thermodynamic expressions
‘enthalpy of combustion’ and ‘enthalpy of vaporization’ superior?
Heat of combustion is the measure of the amount of energy released in the form of heat
(q) when one mole of a substance is burned (combustion).
Latent heat of vaporization is a physical property of a substance. It is defined as the heat
required changing one mole of liquid at its boiling point under standard atmospheric
pressure. It is expressed as kg/mol or kJ/kg.
4.1 Explain why the entropy of a gas increases (a) with volume, (b) with temperature.

If Vf > Vi, as in an expansion, then Vf /Vi > 1 and the logarithm is positive. Consequently,
the eqn predicts a positive value for ΔS, corresponding to an increase in entropy.

When Tf > T i, Tf / Ti > 1, which implies that the logarithm is positive, that Δ S > 0, and
therefore that the entropy increases as the temperature is raised.
The higher the heat capacity of the substance, the greater the change in entropy for a given
rise in temperature.

4.2 Why (in thermodynamic and molecular terms) should substances with high heat
capacities have high entropies?
The higher the heat capacity of the substance, the greater the change in entropy for a given
rise in temperature. A high heat capacity implies that a lot of heat is required to produce a
given change in temperature, so the ‘sneeze’ must be more powerful than for when the
heat capacity is low, and the entropy increase is correspondingly high.

4.3 Justify Trouton’s rule. What are the sources of discrepancies?


Trouton noticed that ∆vapH/Tb)/Tb is approximately the same for all liquids except when
hydrogen bonding or some other kind of specific molecular interaction is present.
Trouton’s rule is explained if all liquids have approximately the same entropy of
vaporization at their boiling points. This near equality is to be expected, because when a
liquid vaporizes, the compact condensed phase changes into a widely dispersed gas that
occupies approximately the same volume whatever its identity.

The exceptions to Trouton’s rule include liquids in which the interactions between
molecules result in the liquid being less disordered than a random jumble of molecules.

4.4 Justify the identification of the statistical entropy with the thermodynamic entropy.
-Statistical entropy basically refers to entropy as the microstate of a energy disperses. A
more uniform microstate will have a small entropy, a more dispersed microstate will have
a higher entropy
-Thermodynamic Entropy refers to the heat transfer affecting the entropy. For example, a
solid turning into a liquid will have a high heat transfer and therefore a greater entropy. (
If you think about it, the transition of solid to liquid can also be seen as the dispersement
of microstates from more uniform to more dispersed.)

4.5 Under what circumstances may the properties of the system alone be used to identify
the direction of spontaneous change?
We shall now show that the apparent driving force of spontaneous change is the tendency
of energy and matter to become disordered. For example, the molecules of a gas may all be
in one region of a container initially, but their ceaseless disorderly motion ensures that
they spread rapidly throughout the entire volume of the container. Because their motion is
so disorderly, there is a negligibly small probability that all the molecules will find their
way back simultaneously into the region of the container they occupied initially. In this
instance, the natural direction of change corresponds to the dispersal of matter.
A similar explanation accounts for spontaneous cooling, but now we need to consider the
dispersal of energy rather than that of matter. In a block of hot metal, the atoms are
oscillating vigorously and the hotter the block the more vigorous their motion. The cooler
surroundings also consist of oscillating atoms, but their motion is less vigorous. The
vigorously oscillating atoms of the hot block jostle their neighbours in the surroundings,
and the energy of the atoms in the block is handed on to the atoms in the surroundings.
The process continues until the vigour with which the atoms in the system are oscillating
has fallen to that of the surroundings. In this case, the natural direction of change
corresponds to the dispersal of energy.

4.6 The evolution of life requires the organization of a very large number of molecules into
biological cells. Does the formation of living organisms violate the Second Law of
thermodynamics? State your conclusion clearly and present detailed arguments to support
it.
The organism is an integral system that functions as a means for the constant exchange
with the environment and its metabolism, where the manifest is the laws of
thermodynamics. 2nd Law of Thermodynamics postulated that every spontaneous process
resulted in a net increase in entropy or disorder, of the system plus its surroundings. This
is known for manifest, for example, in the metabolism.

5.1 Why does the chemical potential vary with (a) temperature, (b) pressure?
(a) For small changes in temperature, the change in molar Gibbs energy at constant
pressure is

At low temperatures, the solid phase has the lowest molar Gibbs energy and is therefore
the most stable. However, as the temperature is raised, the molar Gibbs energy of the
liquid phase falls below that of the solid phase, and the substance melts. At even higher
temperatures, the molar Gibbs energy of the gas phase plunges down below that of the
liquid phase, and the gas becomes the most stable phase. In other words, above a certain
temperature, the liquid vaporizes to a gas.

(b) When the temperature is held constant and the pressure is changed by a small amount
Δp, the molar Gibbs energy of a substance changes by

All molar volumes are positive, the molar Gibbs energy increases (ΔGm > 0) when the
pressure increases (Δp > 0). We also see that, for a given change in pressure, the resulting
change in molar Gibbs energy is greatest for substances with large molar volumes.

5.2 Discuss the implication for phase stability of the variation


of chemical potential with temperature and pressure.
5.3 Without doing a calculation, decide whether the presence
of (a) attractive, (b) repulsive interactions between gas
molecules
will raise or lower the molar Gibbs energy of a gas
relative
to its ‘perfect’ value.
5.4 Explain the significance of the Clapeyron equations and
of the Clausius–Clapeyron equation.
5.5 Use the phase rule to discuss the form of the phase diagram
of sulfur, which has two solid phases, one liquid phase,
and
one vapour phase. Identify the number of degrees of
freedom
for each possible combination of phase equilibrium.
5.6 Explain what is meant by the ‘structure of a liquid’.

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