Chapter 5: The Thermodynamic Description of Mixtures

• Partial molar quantities

• Volume
• Gibbs Energy (Chemical Potential)
• Gibbs-Duhem Equation

• Thermodynamics of Mixing
• Henry’s Law
• Raoult’s Law

• Colligative properties

PHYSICAL CHEMISTRY: QUANTA, MATTER, AND CHANGE 2E| PETER ATKINS| JULIO DE PAULA | RONALD FRIEDMAN
©2014 W. H. FREEMAN D COMPANY
 Partial Molar Volume

• The partial molar volume is something like an effective

molar volume,
VJ = (∂V/∂nJ)p,T,n′

and is often denoted by 𝑉ഥ𝐽 .

• Partial molar properties of a mixture depend on what else

is in the mixture as much as the substance in question.

• For a two-component solution, from slope equation at

constant T and P, change in V is

𝜕𝑉 𝜕𝑉
𝑑𝑉 = d𝑛𝐴 + d𝑛𝐵
𝜕𝑛𝐴 𝑃,𝑇,𝑛𝐵
𝜕𝑛𝐵 𝑃,𝑇,𝑛𝐴

= 𝑉ത𝐴 𝑑𝑛𝐴 + 𝑉ത𝐵 𝑑𝑛𝐵

• 𝑉𝐽 s are constant at constant concentration

• Can change amount of solution, but not concentration,

by increasing moles of components by dn, proportional
to the amount already there:

d𝑛𝐴 = 𝑛𝐴 𝑑𝜆 and d𝑛𝐵 = 𝑛𝐵 𝑑𝜆

• The change in V becomes: 𝑑𝑉 = 𝑉ത𝐴 𝑛𝐴 𝑑𝜆 + 𝑉ത𝐵 𝑛𝐵 𝑑𝜆

• Integration gives V of solution: 𝑉 = 𝑉ത𝐴 𝑛𝐴 + 𝑉ത𝐵 𝑛𝐵

 Partial Molar Volumes

• Why is partial molar volume different from

molar volume?

If a bushel of oranges is mixed with a bushel of

apples, get ~2 bushels of fruit, i.e., DmixV = 0

If a bushel of oranges is mixed with a bushel of

sand, get less than 2 bushels, i.e., DmixV < 0
 Partial Molar Quantities
Partial Molar Property: Thermodynamic quantity that indicates how an extensive property of a solution or
mixture varies with changes in molar composition at constant T, P.
• For a phase of one component, partial molar quantities are identical with molar quantities.

• For an ideal gas or liquid solution, certain partial molar quantities (𝑉ത𝑖 , 𝑈
ഥ𝑖 , 𝐻
ഥ𝑖 ) are equal to sum of the
respective molar quantities for the pure components, while others (𝑆𝑖ҧ , 𝐺ҧ𝑖 , 𝐴ҧ𝑖 )--all related to entropy-- are not.
• For a non-ideal solution, all partial molar quantities differ from the corresponding molar quantities.

• Differences are of interest because they arise from intermolecular interactions

• Every extensive property has a corresponding partial molar property, but , 𝐺ҧ𝑖 , gets a special name and
symbol: the chemical potential, .

By the same argument we found the total volume as a function of partial molar volumes, the Gibbs energy
of a binary solution is given by
𝐺 = 𝑛𝐴 𝜇𝐴 + 𝑛𝐵 𝜇𝐵
 Chemical Potential
With T,P, and n, use slope formula for G:

𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇 + 𝜇𝐴 𝑑𝑛𝐴 + 𝜇𝐵 𝑑𝑛𝐵 + ⋯

which is the fundamental equation of chemical

thermodynamics!

Chemical potential is the slope of a plot of G vs.

nA at constant T,P,n’:
𝜕𝐺
𝜇𝐽 =
𝜕𝑛𝐽 𝑇,𝑃,𝑛′

At constant T and P, slope equation

becomes 𝑑𝐺 = 𝜇𝐴 𝑑𝑛𝐴 + 𝜇𝐵 𝑑𝑛𝐵 + ⋯

Recall that at constant T, P Gibb’s energy gives

maximum non-PV work: 𝑑𝐺 = 𝑑𝑤𝑛𝑜𝑛𝑃𝑉,𝑚𝑎𝑥 .
 What is Chemical Potential?
•  shows how G of system changes when a substance added. If  > 0, G ↑ as n ↑.

• For a pure material,  is just free energy/mole, Gm = G/n.

• (For a mixture  ≠Gm)

Not only does  show how G changes when n changes, but how U & H change (but under different conditions):
G  U  PV TS U  G  PV TS

dU  dG  PdV VdP  TdS SdT U 

At constant V and S,    
n S,V
dG  VdP  SdT  dn

dU  PdV  TdS  dn

In fact,  shows how U, H, A, and G depend on composition. For example, can show:

H 
   
n S,P
 Potential Displacement
• For this reason,  is central to chemistry.
Pressure Volume
Gravity Height
• Can think of contributions to G in terms of pairs of Voltage Charge
variables: Chemical potential Moles

• If in system there is a difference in column A, column B will change until the difference is 0.

• Can think of  as the potential for moving material.

• If the chemical potential in one region of a system is different from that in another region, material will be
transferred until the potential difference = 0. All chemical potentials in a system are equal at equilibrium.
 Gibbs-Duhem Equation
Describes the relationship between changes in chemical potential for components in a mixture.
Since 𝐺 = 𝑛𝐴 𝜇𝐴 + 𝑛𝐵 𝜇𝐵 , the total derivative of G is: d𝐺 = 𝑛𝐴 𝑑𝜇𝐴 + 𝑑𝑛𝐴 𝜇𝐴 + 𝑛𝐵 𝑑𝜇𝐵 + 𝑑𝑛𝐵 𝜇𝐵
But at constant T and P, 𝑑𝐺 = 𝜇𝐴 𝑑𝑛𝐴 + 𝜇𝐵 𝑑𝑛𝐵
Setting the two equations for dG equal (since G is a state function):
𝑛𝐴 𝑑𝜇𝐴 + 𝑛𝐵 𝑑𝜇𝐵 = 0

This is a specific case of the Gibbs-Duhem Equation:

෍ 𝑛𝐽 𝑑𝜇𝐽 = 0
𝐽
𝑛𝐴
𝑑𝜇𝐵 = − 𝑑𝜇𝐴
𝑛𝐵
The chemical potential of one component in a mixture
cannot change independently of the chemical potentials of
the other components!
True of all partial molar quantities.
Used in practice to determine the partial molar volume of
one component in a binary mixture when the partial molar
volume of another component is known.
 Thermodynamics of mixing, Gibbs Free Energy
𝜃 𝑃 𝑃
From 𝐺𝑚 𝑃 = 𝐺𝑚 + 𝑅𝑇𝑙𝑛 , 𝜇 𝑃 = 𝜇𝜃 + 𝑅𝑇𝑙𝑛
𝑃𝜃 𝑃𝜃
where 𝜇𝜃 is the standard chemical potential (1 bar)
• Before mixing (initially at same T & P)
Ginit   AnA   B nB

 n A (  A  RT ln( P / P ))  nB (  B  RT ln( P / P ))
• After mixing
G fin  n A (  A  RT ln( PA / P ))  nB (  B  RT ln( PB / P ))

• Free energy of mixing for an ideal gas:

DGmix  nA RT ln( PA / P)  nB RT ln( PB / P)

 nRT ( xA ln xA  xB ln xB )
Because mole fractions (xi) are always ≤ 1, for a perfect
gas, ∆mixG < 0, i.e., perfect gases mix spontaneously.
 Thermodynamics of mixing, Entropy and Enthalpy
• Entropy of mixing:
 DGmix 
Since 𝜕𝐺 Τ𝜕𝑇 𝑃,𝑛 = −𝑆, then    DS mix
 T 
DSmix  nR( xA ln xA  xB ln xB )
• Enthalpy of mixing (at constant T, P):

DH mix  DGmix  TDSmix  0

• The DmixV (V of solution - Vs of components):


D mix V  V  n1Vm1
*
 n2V *m2 
• Combining equations:

V*m,i - molar Vol. of pure liquid

V  n1V1  n2V2

D mix V  n1 V1  Vm1
*
 
 n2 V 2  V m2
*

Calculate DmixG and DmixS for mixing 3 moles of H2 and 1 mole of N2 at 298.15 K.
If the initial pressure of N2 is p, then that of H2 is 3p.
Thus, the initial Gibbs energy is:
Gi  (3.0 mol )[  o ( H 2 )  RT ln 3 p  (1.0 mol )[  o ( N 2 )  RT ln p]
After the partition is removed, the initial partial pressures of
both gases are halved, and the Gibbs energy changes to:
The Gibbs energy of mixing is then ∆mixG = Gf – Gi or:
D mixG  nRT ( xA ln xA  xB ln xB )
3/ 2p 1/ 2 p
D mix G  (3.0 mol ) RT ln  (1.0 mol ) RT ln
3p p
 (3.0 mol ) RT ln 2  (1.0 mol ) RT ln 2
 (4.0 mol ) RT ln 2  6.9 kJ
 D mix G 
D mix S       nR ( x A ln x A  xB ln xB )
 T  p ,nA ,nB
All of the driving force for mixing comes from
 D mix G  the increase in entropy of the system, because
    23.1 J/K
 T  the entropy of the surroundings is unchanged.
 Chemical potentials of liquids
Pure A (l) in A(l) in a mixture in
equilibrium with its PA* PA equilibrium with vapor.
vapor.  ( g )  RT ln

 ( g )  RT ln

A
P A
P
(Pure substances are
denoted with a *.)
 * (l )  (l )
A
A

Pure A Mixture of A & B

PA* 
PA

 (l )   ( g )  RT ln
*
 (l )   ( g )  RT ln
A A
P  A
P

At equilibrium, the two chemical potentials of A are equal:

 PA 
 A (l )   A (l )  RT ln * 
*
P 
 A
A solution for which the partial vapor pressure of
each volatile component is directly proportional to
its mole fraction in the liquid phase obeys Raoult's
Law, and is said to be an ideal solution:

PA  x A PA*

 (l )   * (l )  RT ln x A
A A

Raoult’s Law can be applied quantitatively for

solutions in which the molecules of the various
components are similar in size, shape, and
intermolecular forces.

Raoult’s Law should not be confused with

Dalton’s Law, which relates partial pressures of
gases to their mole fractions in the vapor phase:
Pi  Yi P
Solutions of chemically similar liquids Solutions of chemically dissimilar liquids
behave nearly ideally deviate from ideality
 Henry's Law
In ideal solutions the solute, as well as the solvent, obeys
Raoult’s Law. But at low concentrations of solute,
although vapor pressure of solute is proportional to its
mole fraction, the constant of proportionality is not the
vapor pressure of the pure substance, but is the so-called
Henry’s Law constant: PB = xBKB

where PB is the vapor pressure of the solute, xB is its

mole fraction, and the empirical Henry’s Law constant,
KB has the dimensions of pressure.

Mixtures for which the solute obeys Henry’s Law and

the solvent obeys Raoult’s Law are termed ideal-dilute
solutions.
Henry’s Law is essentially a limiting law, since
𝑃𝐵
𝐾𝑋 = lim
𝑋𝐵 →0 𝑋𝐵

and can also be expressed in other concentration units:

𝑃𝐵 𝑃𝐵
𝐾𝑚 = lim or 𝐾𝑐 = lim
𝑚→0 𝑚 𝑐→0 𝑐
Henry’s Law behavior arises from the fact that in very • Henry’s Law works well when the gas is only
dilute solutions, the environment of the solvent molecules sparingly soluble in the solvent, behaves ideally,
is virtually the same as that in the pure liquid. However, and does not ionize or otherwise react with the
the environment of the solute molecules is very different solvent.
from that in the pure state, since they are surrounded by
solvent molecules. • Similar to Raoult's Law, and is exactly the same for
an ideal solution with PB*= KB. (Fig. 5A.14)

• Henry's Law applies only to dilute solutions.

• Raoult's Law is applicable at high concentrations

of solvent.
Vapor Pressure Diagrams for Real Solutions
 Thermodynamics of Mixing of Ideal Solutions
In an ideal solution, the chemical potential of each component, J, is given by the same expression as that used
previously for the mixing of two gases:
 (l )   * (l )  RT ln xJ
J J

The total Gibbs energy before the liquids are mixed is:

Gi  nA  *A  nB  B*
where the * denotes the pure liquid.

After mixing, the total Gibbs energy (assuming an ideal solution) is:

G f  nA (  *A  RT ln x A )  nB (  B*  RT ln xB )

The Gibbs energy of mixing is then Gf – Gi:

D mix G  nA ( RT ln x A )  nB ( RT ln xB )  nRT ( x A ln x A  xB ln xB )
As for gases, the ideal entropy of mixing two liquids is then given by:

D mix S  nR ( x A ln x A  xB ln xB )
and, as was also true for gas mixtures, the enthalpy of mixing in an ideal solution is zero, since

D mix G  D mix H  T D mix S

then

D mix H  D mix G  T D mix S  0

It should be noted that the change in volume upon mixing (∆mixV) is also zero because ∆mixG for an
ideal mixture is independent of pressure, i.e., (∂Gmix/∂p)T = Vmix.

Thus, the thermodynamic conclusions for mixing in an ideal solution are similar to those for perfect gases,
although the assumptions are different. In a perfect gas, it is assumed that there are NO intermolecular
interactions. In an ideal solution, it is assumed that A-A, B-B, and A-B interactions are the same.
 Deviations from Raoult's Law
Raoult's Law is purely statistical - chemical behavior is found in deviations from statistical behavior.
Deviations discussed in terms of excess thermodynamic functions: XE = DmixX – DmixXideal

Regular Solution Theory

Excess Enthalpy SE=0; HE = nRTxAxB, where  depends on energy of A-B interactions, relative to A-A interactions

 < 0: mixing is exothermic, i.e.,

A-B interactions are more favorable
than A-A or B-B interactions, e.g., the
mixture forms H-bonds

 > 0: mixing is endothermic, i.e., A-B

interactions are less favorable than A-A
or B-B interactions, e.g.,
H-bonds are disrupted; extreme case:
immiscibility

Thus, ∆Gmix becomes: DGmix  nRT ( x A ln x A  xB ln xB   x A xB )

 Colligative properties
Colligative Property: A solution property that depends only on the number of solute molecules or ions
present and not on any specific chemical property of the solute (i.e., on the mole fraction of the solute, not on
its chemical identity.)

• vapor pressure lowering

• boiling-point elevation
• freezing-point depression
• osmotic pressure

• These changes in solution are in response to the changes in chemical potential of the liquid solvent by the
addition of solute molecules to the pure solvent.

• These methods historically used for determining molecular weights. (modern methods: mass spectrometry
and gel-permeation chromatography)

The phenomenon of colligative properties is essentially an entropy effect, i.e., the addition of solute
particles (molecules or ions) increases the disorder and, hence, the entropy of the solvent compared to the
pure solvent.
 Boiling Point Elevation
For solvent vapor in equilibrium with a solution of a non-volatile solute:
 *A ( g )   *A ( )  RT ln x A
Rearranging: D vap G
 *A ( g )   *A ( )
ln x A  
RT RT
Taking the derivative of both sides with respect to temperature:

d ln x A 1 (D vap G / T ) D vap H
 
dT R dT RT 2
where the Gibbs-Helmholtz equation [((∂G/T)/∂T)p] was used to express the term on the RHS. Then multiply
both side by dT and integrate from xA = 0 to xA

1 T D vap H
ln x A


ln( x A 1)
d ln x A    *
R T T 2
dT

where T* is the normal boiling point of the pure solvent.

The LHS integrates to ln xA , which equals ln(1 - xB). Thus, assuming that ∆vapH is constant over the
typically very small temperature range between T* and T,
D vap H T 1 D vap H  1 1 
ln(1  xB )  
R T * T 2 dT  R  T  T * 
It can be shown (Justification 5B.1), using the approximations T ≈ T* and xB << 1, that the above
equation results in *2
RT
T – T* = ∆Tb = KbxB =  xB
D vap H
where ∆Tb is the elevation in boiling point of the pure solvent caused by the presence of the solute B
at a mole fraction of xB . The so-called boiling point elevation constant, Kb, is an empirical constant
that is related to ∆vapH of the pure solvent and is unique for each solvent.

Because the mole fraction xB is directly proportional to the molality b (moles of solute per kg of
solvent) of the solution, the latter concentration unit is usually used for boiling point elevation
measurements.
 Freezing Point Depression

Using an analysis analogous to that for boiling point elevation, it can be shown that for a solution in
equilibrium with a pure solid solvent, the melting point of the solid solution is lower than that of the pure
solid solvent:
 *A ( s )   *A ( )  RT ln x A
which leads to:
RT *2
∆Tf = KfxB =  xB
D fus H
where T* is the normal melting point of the pure solid
solvent, and Kf is the freezing-point depression
constant.

As was the case for the boiling point elevation

constant, Kf is an empirical constant that is related to
∆fusH of the pure solid solvent.
 Osmotic Pressure
Osmosis is the spontaneous passage of a pure solvent into a solution of the solvent separated from it
by a semipermeable membrane, i.e., one that allows passage of solvent molecules through it, but not
solute particles (molecules or ions). The pressure that must be applied to the solution to prevent
passage of the solvent through the membrane is referred to as the osmotic pressure, Π.
Because the chemical potential of the pure solvent (A) is larger than that of the solvent in the solution, the
driving force for osmosis is to decrease μA (i.e., decrease the Gibbs energy and increase the entropy) in the
pure solvent until it equals that in the solution, and the system is at equilibrium.

In essence, the applied osmotic pressure, Π, on the solution side of the membrane increases μA in the
solution until it equals that in the pure solvent. Hence, at equilibrium,

 *A ( p)   *A ( x A , p   )

As shown in Justification 5B.3, the osmotic pressure needed to equalize μA on both sides of the membrane
is given by the van’t Hoff Equation:
Π = [B] RT

where [B] = nB/V is the molar concentration, i.e. the molarity, of the solute, B, in the solvent A. When
expressed in the following form, the van’t Hoff Equation clearly resembles the perfect gas equation:

Π Vm = RT xB

since, when the solution is dilute, xB = nB/nA. and nAVm = V, the total volume of the solution.
 Use of Osmotic Pressure
Because osmotic pressure effects are very large compared to freezing point depressions and are relatively
easy to measure, they are used to determine molecular weights of macromolecules, such as synthetic
polymers and proteins.

Example: For a solute having a M.W. of 40,000 g/mol,

in an aqueous solution with a concentration of 5 x 10-6 molar.

• Freezing Point Depression Method:

∆Tf = Kfb = 1.86 (5 x 10-6) = 9 μK
very difficult to measure!

• Osmotic Pressure Method:

Π ≈ cRT ≈ (5 x 10-6) (0.082) (298) ≈ 1.2 x 10-4 atm
= 0.093 mm Hg = 1.3 mm H2O

• Problems with osmotic pressure measurements:

- Must use correct membrane
- Times needed to reach equilibrium may
be very long (hours to days!)
 Vapor Pressure Diagrams

For a two-component ideal solution containing the

volatile liquids A and B, the partial vapor pressures
are given by Raoult’s Law:

pA = xAp*A and pB = xBp*B

where p*A is the vapor pressure of pure A and p*B

that of pure B. Therefore, the total vapor pressure
p of the mixture is:

p = pA + pB = xAp*A + xBp*B = p*B + (p*A – p*B)xA

Thus, at constant T, the total vapor pressure of the

mixture changes linearly from p*B to p*A as xA varies
from 0 to 1, as shown in Fig. 5C.1.
 Vapor Pressure Diagrams

The partial pressures of A and B in the gas-phase that is in

equilibrium with the liquid mixture are given by Dalton’s
Law:
pA = xAp and pB = xBp

Thus, the mole fractions, yi, in the gas phase are:

pA pB
yA  and yB 
p p
Thus, if the solution is ideal, the partial pressures, pi, and
the total pressure, p, can be expressed in terms of the mole
fractions, xi, in the liquid:
x A p*A
yA  * yB  1  y A (Eq. 5C.4)
pB  ( p A  pB ) x A
* *

As shown in Fig. 5C.2, because A is the more volatile

component, yA > yB at all compositions, for pA* ≥ pB*.
 Vapor Pressure Diagrams

Because the composition of the liquid can be

related to the composition of the vapor via
Raoult’s Law (pi = xip*i) and yi = pi/p, the total
vapor pressure, p, can be related to the
composition of the vapor:
p*A pB*
p *
p A  ( pB*  p*A ) y A

As shown in Fig. 5C.3, the total vapor

pressure is largely determined by that of the
more volatile component, A.
 Vapor Pressure Diagrams

Figs. 5C.2 and 5C.3 can be combined into a single Figure

that shows the total system composition (both liquid and Tie Line
vapor) for one of the components, represented by zA. In the
region labeled “Liquid” the applied pressure is sufficiently
high (higher than p*A) that only the liquid phase exists, so
zA = xA.

Similarly, in the region labeled “Vapor” the pressure is

sufficiently low that only the vapor phase exists, so zA = yA.

Between the two lines, both liquid and vapor phases exist,
where, at any point, a horizontal line (called a tie line)
connects the mole fraction of A in the liquid phase, xA, with
that in the vapor phase, yA.
 Vapor Pressure Diagrams
a 1 , a1 ‘ a3, a3’ a4

Isopleth
Vapor Pressure Diagrams
Vapor Pressure Diagrams
 The Lever Rule

Any point in the two-phase region of a vapor-liquid

phase diagram represents quantitatively the relative
amounts of the two phases. The amounts, nα and
nβ, of the phases α (vapor) and β (liquid), that are in
equilibrium, for example, can be determined by
measuring the distances lα and lβ along the
horizontal tie line and then applying the so-called
lever rule:
nα lα = nβ lβ

For example, the two lengths lα and lβ from the

central point on the tie line in Fig. 5C.9 are
approximately equal, indicating that the relative
amounts, nα and nβ, of the α (vapor) and β (liquid)
phases at this composition are also approximately
equal at equilibrium.
Distillation
 Distillation

Vapor
Vapor Composition
Composition

Boiling Temp.
of Liquid
Boiling Temp.
of Liquid
 Azeotropes

A-B interactions are more favorable than A-A and A-B interactions are less favorable than A-A and
B-B interactions (GE < 0), thus decreasing V.P. of B-B interactions (GE > 0), thus increasing V.P. of
mixture and increasing B.P. In effect the favorable mixture and decreasing B.P. Unfavorable A-B
A-B interactions stabilize the liquid. interactions destabilize the liquid.
 Deviations from Raoult's Law
Raoult's Law is purely statistical - chemical behavior is found in deviations from statistical behavior.
Deviations discussed in terms of excess thermodynamic functions: XE = DmixX – DmixXideal

Regular Solution Theory

Excess Enthalpy SE=0; HE = nRTxAxB, where  depends on energy of A-B interactions, relative to A-A interactions

 < 0: mixing is exothermic, i.e.,

A-B interactions are more favorable
than A-A or B-B interactions, e.g., the
mixture forms H-bonds

 > 0: mixing is endothermic, i.e., A-B

interactions are less favorable than A-A
or B-B interactions, e.g.,
H-bonds are disrupted; extreme case:
immiscibility

Thus, ∆Gmix becomes: DGmix  nRT ( x A ln x A  xB ln xB   x A xB )

The maximum concentration of ethanol
that can be obtained by fractional
distillation of an ethanol-water mixture
is a low-boiling azeotrope that is
95.63% ethanol by mass and boils at
78.2oC, which is lower than the boiling
points of either ethanol (78.4oC) or
water (100oC).
Distillation of Immiscible Liquids
Liquid-Liquid Phase Diagrams

nAlA
nBlB
 Liquid-Liquid Phase Diagrams

A mixture of 50 g (0.59 mol) of n-hexane and 50 g

(0.41 mol) of nitrobenzene at 290K occurs in the
Tuc
two-phase region of the phase diagram. One of the
phases (the purple line) is hexane-rich, and the
other (the blue line) is rich in nitrobenzene. The
amounts of the two phases are given by the lever
rule applied to the endpoints of the tie line at
290K:
n l nH lN 0.83  0.41 0.42 0.35 0.41 0.83
     7
n l nN lH 0.41  0.35 0.06
Thus, there is ~7 times more of the hexane-rich
phase than of the nitrobenzene-rich phase.

If a sample with xN = 0.41 were heated to 292K or

higher, the two phases would become a single
phase.
Liquid-Liquid Phase Diagrams
Liquid-Liquid Phase Diagrams
 Solid-Liquid Phase Diagrams
Simplest type of binary solid-liquid phase diagram
is one in which both components are completely
miscible in both the liquid and solid phases. This
type of system is called isomorphous.

Example is copper-nickel, for which the phase

diagram has only a very narrow two-phase (Liquid
+ Solid) region. Copper and nickel are completely
miscible in all proportions and form true alloys,
not merely physical admixtures.

The line above which the mixture is a liquid is

called the liquidus line. At temperatures just
below this line, crystals of a solid solution begin
forming.

The line below which solidification is complete is

called the solididus line. At temperatures below
this line, only a solid solution exists.
 Solid-Liquid Phase Diagrams
For cooling along the isopleth beginning at a1,

a1→a2: System enters two-phase region “Liquid + B”.

Pure solid B begins to come out of solution,
and remaining liquid becomes richer in A.

a2→a3: More solid B forms. Relative amounts of solid

and liquid (approximately equal at this point)
given by Lever Rule along tie line.
Composition of Liquid phase given by b3.

a3→a4: At a4, there is less liquid than at a3, and its

composition is given by e2. At the temperature
of e2 and below, the remaining liquid solidifies
to give a two-phase system containing an
admixture of (almost) pure A and pure B.

The isopleth at e2 corresponds to a eutectic composition, i.e., the mixture of A and B with the lowest M.P.
Solutions to the right of e2 deposit pure B as they cool, while those to the left deposit pure A.
Solid-Liquid Phase Diagrams
Solid-Liquid Phase Diagram of Tin-Lead
 Electron Micrographs of Metal Mixtures

Scale Line = 250μ Scale Line = 125μ Scale Line = 25μ

Solid-Liquid Phase Diagram of NaCl-H2O
 Melting Behaviors of Mixtures
fp lowering fp lowering
of A by B of B by A
• Eutectic - minimum melting point; two curves intersect
• Solid solutions Liquid
fp of A
atomic-level random mixture composition variable melting Solid A+ Solid B+
fp of B
point is not sharp. T Liquid Liquid

• Compound formation Eutectic

Convention: A vertical line on a two-component phase- Solid A + Solid B
diagram denotes the formation of a compound.
XB

• Incongruent Melting Points - some compounds do not Liquid fp of B

melt into a liquid of the same composition, but Solid B+
Liquid
decompose into another solid. fp of A
Solid A+ Solid C+
T Liquid Liquid
Solid B+
Solid C
Eutectic
Compound
Solid A + Solid C
Formation

A C B
XB
 Solid-Liquid Phase Diagrams

962oC

232oC
Solid-Liquid Phase Diagrams
Zn-Mg Phase Diagram

What is the melting temperature of the

eutectic between Mg and MgZn2?

A. 410
B. 590
C. 347
D. 650
Na-K Phase Diagram