ENGINEERING MATERIAL

GIBBS EQUATION (GIBBS PHASE RULE), STACKING RATIO (IONIC

PACKING FACTOR) AND VOLTS SERIES

ASIGNMENT No.1

By

HASSAN KHAMIS HASSAN

ID No. U100170009

2018
 GIBB’S EQUATION (GIBBS PHASE RULE)

Gibb’s Phase Rule

Gibb’s phase rule describes the thermodynamic state of a material. This famous rule is used

to determine the number of phase that can coexist in equilibrium in a given system.

A rule stating that; the number of degrees of freedom in a closed physical system

at equilibrium is equal to the numberof chemical components minus the number of phases

plus the constant 2.

It has general form: F = C – P + 2 or F + P = C + 2

F is number of degrees of freedom, or number of variables, such as temperature, pressure, or

composition that are allowed to change independently without changing the number of phase

in equilibrium.

C is number of components, usually elements or compounds in the system.

P is number of phases presents. Phase is defined as any homogeneous and physically distinct

part of a system having physical and chemical properties the same through the system.

2 is constant in the equation implies that both temperature and pressure are allowed to

change.
Significant of Gibbs Phase Rule

o It provides a simple method of classifying equilibrium states of systems.

o It is applicable only to macroscopic systems and hence no information is required

regarding molecular or micro structure.

o It takes no account of nature of the reactants or products in phase reactions.

o It predicts the behaviour of systems with changes in the variables that govern the

system in equilibrium.

Example, the Water System

Water exists in 3 possible phases, namely solid ice, liquid water and water- vapour.

Hence, there can be three forms of equilibria, each involving two phases such as.

Solid Ice Liquid Water

Liquid Water Water - vapour

Solid Ice Water - vapour

Consider the phase diagram for the water system in fig. 1, it contains curves, areas, and

triple point.

Figure 1 Components of water system

Curve OA

 The curve OA is called vapourisation curve, it represents the equilibrium between

water and vapour.

 At any point on the curve the following equilibrium will exist.

Liquid Water Water - vapour

 This equilibrium ( i.e. line O A ) will extend up to the critical temperature

(374°C).

 Beyond the critical temperature the equilibrium will disappear and only water

vapour will exist.

Curve OB

 The curve OB is called sublimation curve of ice, it represents the equilibrium

between solid ice and water-vapour.

 At any point on the curve the following equilibrium will exist.

Solid Ice Water - vapour

 This equilibrium (i.e. line OB) will extend up to the absolute zero (− 273°C)

 Beyond absolute zero only solid ice will exist and no water-vapour.

Curve OC

 The curve OC is called melting point curve of ice, it represents the equilibrium

between ice and water.

 At any point on the curve the following equilibrium will exist.

Solid Ice Liquid Water

 The curve OC is slightly inclined towards pressure axis. This shows that melting

point of ice decreases with increase of pressure.

 Curve OB′ (Metastable Equilibrium)

 The curve OB′ is called vapour pressure curve of the super-cooled water (or)

metastable equilibrium where the following equilibrium will exist.

Super- cooled water Water – vapour

 Sometimes water can be cooled below its freezing point (0°C) without the

formation of ice, this water is called super-cooled water.

 Super cooled water is unstable and it can be converted into solid ice by “seeding”

(or) by slight disturbance.

Along the curves OA, OB, OC and OB′

The number of phases (P) is 2 component (C) is 1 and the degree of freedom of the

system is one. This is predicted by the phase rule:

F= C− P+ 2

F=1−2+2

F=1

Therefore, either temperature (or) pressure must be fixed to define the system.

Point ‘O’ (Triple point)

 The three curves OA, OB and OC meet at a point “O”, where three phases namely

Solid ice, liquid water and water-vapour are simultaneously at equilibrium.

 This point is called triple point, at this point the following equilibrium will exist

Ice (s) Water (l) Vapour (g)

At this point the no. of phases (P) is 3, component(C) is 1 and the degree of freedom of

the system is zero. This is predicted by the phase rule:

 F= C − P+ 2

F= 1 − 3 + 2

F= 0

This takes place only at a constant temperature (0.0075°C) and pressure (4.58 mm of
Hg).

Areas

An AREA AOC, BOC, AOB represents liquid water, solid ice and water-vapour

respectively where the no. of phases (P) and component(C) are one. Hence the degree of

freedom of the system is two. This is predicted by the phase rule:

F= C − P+ 2

F= 1 − 1 + 2

F= 2

Therefore, both temperature and pressure must be fixed to define the system at any

point in the areas.

 STACKING RATIO

(IONIC PACKING FACTOR/ATOMIC PACKING ACTOR)

Atomic packing factor (APF) or packing efficiency indicates how closely atoms are packed in

a unit cell and is given by the ratio of volume of atoms in the unit cell and volume of the unit

cell.

𝐕𝐨𝐥𝐮𝐦𝐞 𝐨𝐟 𝐚𝐭𝐨𝐦𝐬
APF =
𝐕𝐨𝐥𝐮𝐦𝐞 𝐨𝐟 𝐮𝐧𝐢𝐭 𝐜𝐞𝐥𝐥

Atomic packing factor for FCC

In the FCC unit cell effective number of atoms = 8 corner atoms x (1/8) (each atom is shared

by 8 unit cells) + 6 face-centered atoms x1/2 (each shared by two unit cells) = 4

1
F 2

3 C

Figure 2 Cubic Packed Structures

The corner atom C is shared by unit cells 1, 2, 3, 4 and four more in front of each of them.

The face-centered atom, F is shared between cells 1 and 2.

Considering the atoms as hard spheres of radius, R

4
Total Volume = 4 × πR3
3
The relation between R and the FCC cell side a as shown in the figure below is √2𝑎 = 4R

Figure 3 FCC Packed Structures

3
Volume of atoms 4×43 πR
APF (FCC) = =
Volume of unit cell a3
16× 2 ×a3 √2π
= = 0.74
3×64×a3

Therefore APF of FCC is 0.74.

Atomic packing factor for BCC

For BCC crystals effective number of atoms per unit cell is 8 x 1/8 + 1 = 2 and the relation

between R and a is √3𝑎 = 4R, as shown in the figure below.

Figure 4 BCC Packed Structures

 Hence; APF of BCC is defined by

3
Volume of atoms 2×43 πR
APF (BCC) = =
Volume of unit cell a3
8× 3 ×a3 √3π
= = 0.68
3×64×a3

Therefore APF of FCC is 0.68

Conclusions:

a) In Body Centered Cubic (BCC) metal structure has two metal atoms/unit cell and the

atomic packing factor of 0.68. Since atoms are in contact along the body diagonals of

the unit cell.

b) In Face Centered Cubic (FCC) metal structure has 4 metal atoms/unit cell and the

atomic packing factor is 0.74, hence atoms are in contact along the face diagonal of

the unit cell, therefore the difference between BCC and FCC is metal structure atoms

that can give different value of APF which depend on the diagonal of the unit cell.

c) Furthermore, atoms may assemble into crystalline or amorphous structures, it can

predict the density of a material, provided it’s known the atomic weight, atomic

radius, and crystal geometry (e.g., FCC, BCC)

 VOLTS SERIES

A Voltaic Cell (also known as a Galvanic Cell) is an electrochemical cell that uses

spontaneous redox reactions to generate electricity. In redox reactions, electrons are

transferred from one species to another. To harness this energy, the reaction must be split into

two separate half reactions: the oxidation and reduction reactions. The reactions are put into

two different containers and a wire is used to drive the electrons from one side to the other. In

doing so, a Voltaic/ Galvanic Cell is created.as shown in figure 5 below.

Electrode
M Half -cell
Half -cell

Figure 5 Voltaic Cell

The above figure 5 is a reaction of a solid copper (Cu) in a silver nitrate solution (AgNO3),

by reaction presented by the following equation below.

2Ag+ (aq) + Cu(s) ⇋ Cu2+ (aq) + 2Ag(s)

The AgNO3(s) will dissociate to produce Ag+ (aq) ions and NO3 (aq) ions. The NO3 ions can be

ignored since they are spectator ions and do not participate in the reaction. In this reaction, a

copper (Cu) electrode is placed into a solution containing silver ions. The Ag+ (aq) will readily

oxidize Cu(s) resulting in Cu2+ (aq) while reducing itself to Ag(s).

 n+
Metal ion M from the solution may collide with the electrode, gaining "n" electrons from

it, and convert to metal atoms. This means that the ions are reduced. Metal atom on the

surface may lose "n" electrons to the electrode and enter the solution as the ion M, which

means that the metal atoms are oxidized.

Half Cells are device consisting of a single electrode immersed in an electrolytic solution and

thus developing a definite potential difference.

Wire is a single strand of metal drawn out into the form of a thin flexible thread or rod,

capable transmission of electrons from one side to the other.

Electrodes are strip of metal on which the reaction takes place. In a voltaic cell, the oxidation

and reduction of metals occurs at the electrodes. The two electrodes in a voltaic cell, in each

half-cell, known as cathode and anode.

Cathode is an electrode where reduction takes place. This is where the metal electrode gains

electrons. Referring back to the equation above, the cathode is the Ag(s) as it decreases in

oxidation state from +1 to 0.

Anode is an electrode where oxidation takes place. Here metal loses electrons from

above reaction, the anode is the Cu(s), since it increases in oxidation state from 0 to +2.

Oxidation is the loss of electrons or an increase in oxidation state by a molecule, atom,

or ion.

Reduction is the gain of electrons or a decrease in oxidation state by a molecule, atom, or ion

Molecule is an electrically neutral group of two or more atoms held together by chemical

bonds.

Atom is the smallest constituent unit of ordinary matter that has the properties of a chemical

element.

Ion is an atom or molecule that has a non-zero net electrical charge (its total number of

electrons in element)

Redox Reactions are reactions in which one species is reduced and another is oxidized.
Salt Bridge is a vital component of any voltaic cell. It is a tube filled with an electrolyte

solution such as KNO3(S) Or KCl(S).

The purpose of the salt bridge is to keep the solutions electrically neutral and allow the free

flow of ions from one cell to another. Without the salt bridge, positive and negative charges

will build up around the electrodes causing the reaction to stop.

Voltmeter

A voltmeter, also known as a voltage meter, is an instrument used for measuring the potential

difference, or voltage, between two points in an electrical or electronic circuit.

Flow of Electrons

Electrons always flow from the anode to the cathode or from the oxidation half-cell to the

reduction half-cell. In terms of E cell of the half reactions, the electrons will flow from the

more negative half reaction to the more positive half reaction.

Cell Diagram

A cell diagram is a representation of an electrochemical cell. The figure below illustrates a

cell diagram for the voltaic cell shown in figure 5 above.

Figure 6 Cell diagram

For the drawing a cell diagram, the following easy conventions should be follow:-

1) The anode is always placed on the left side, and

2) The cathode is placed on the right side.

3) The salt bridge is represented by double vertical lines (||).

4) The difference in the phase of an element is represented by a single vertical line (|),

5) The changes in oxidation states are represented by commas (,).

For a Constructing a Cell Diagram

By considering the following reaction;

2Ag+ (aq) + Cu(s) ⇋ Cu2+ (aq) + 2Ag(s)

Follow the following simple instructions.

 Write the two half-reactions

Ag+ (aq) + e− ↔ Ag(s)

Cu(s) ↔ Cu2+ (aq) + 2e−

 Determine the cathode and anode.

Anode: Cu(s) ↔ Cu2+ (aq) + 2e−

Cathode: Ag+ (aq) + e− ↔ Ag(s)

 Cu(s) is losing electrons thus being oxidized. Oxidation happens at the anode

and Ag+ is gaining electrons thus is being reduced. Reduction happens at the

cathode.

 Now, Construct the Diagram as follow :-

Cu(s)| Cu2+ (aq) || Ag+ (aq) | Ag(s)

Furthermore, the anode always goes on the left and cathode on the right. Separate changes

in phase by | and indicate the salt bridge with ||.

Note:

Remembering Oxidation and Reduction

When it comes to redox reactions, it is important to understand what it means for a metal to

be “oxidized” or “reduced”. An easy way to do this is to remember the phrase below:-

OIL = Oxidization Is Loss (of e)

RIG = Reduction Is Gain (of e)

In the case of the example above Ag+ (aq) gains an electron meaning it is reduced. Cu(s)

loses two electrons thus it is oxidized.

REFERENCES

1. http://chemwiki.ucdavis.edu/Analytical_Chemistry/Electrochemistry/Voltaic_Cells.

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4. http://www2.ohlone.edu/people/jklent/labs/101B_labs/Voltaic%20Cells.pdf

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6. https://chem.libretexts.org/Core/Analytical_Chemistry

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John Wiley & Sons Inc 1993

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Publication. 1983.

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