Comments to Lecture 3.

p. 32.

High-temperature solution calorimetry: solution calorimetry (samples are kept at temperature of

calorimeter and then dropped into calorimeter filled with solvent), drop solution calorimetry
(samples are kept at room temperature and then dropped into calorimeter filled with solvent at
temperature T), transposed drop calorimetry (drop of samples kept at room temperature into
calorimeter without solvent at temperature T).

Reaction of formation 0.5La2O3+0.5Y2O3=LaYO3 (1)

La2O3 was kept at 973 K and then dropped to calorimeter cell with T=973 K

La2O3 (s,973 K) → dilute solution of La2O3 in 2PbO·B2O3 H2= -126.0± 4.4 kJ/mol

Y2O3 was kept at 973 K and then dropped to calorimeter cell with T=973 K

Y2O3 (s,973 K) → dilute solution of Y2O3 in 2PbO·B2O3 H3= -61.7±1.1 kJ/mol

LaYO3 was kept at 973 K and then dropped to calorimeter cell with T=973 K

LaYO3(s,973) → dilute solution La2O3 and Y2O3 in 2PbO·B2O3 H4= -38.5±3.0 kJ/mol

H1(973K) = 0.5H2+0.5H3-H4 = -55.35±5.8 kJ/mol

Drop-solution calorimetry

Pure oxides and oxide compound are kept at room temperature and then dropped into calorimeter
with solvent at temperature 973 K.

The data in Table at p. 31 were obtained using solution calorimetry for oxides and their enthalpy
increment was measured by transposed drop calorimetry. The data for the LaYO3 were obtained by
drop-solution calorimetry. Enthalpy increments H(973)-H(298) for oxides H1 and H3 are results of
drop of oxides into calorimeter without solvent.H2 and H4 are heats of dissolution measured for
oxides kept at 973 K and dropped into calorimeter at 973 K. H5 is heat of dissolution together with
enthalpy increment measured by drop of LaYO3 kept at 298 K into the calorimeter at temperature
973 K.

H6(298K)=0.5(H1+H2+H3+H4)-H5= -50.87±4.0 kJ/mol

Drop-solution
calorimeter
consists from two
crucibles in the
cell each one with
dropping tube
and tube for
bobbling of gas
(for better
mixing).
Next example presents results of drop-solution calorimetry used for oxides (TiO2, rutile and ZrO2,
monoclinic) and for compound -ZrTiO4. Sodium molybdate was used as solvent at 973 K.

TiO2(cr,298)+ZrO2(cr,298)=-ZrTiO4(cr,298) H1

TiO2 (cr, rutile,298) = TiO2 (sol,T) (2) ∆HDS(2) = 58.7 ±0.9 kJ/mol

ZrO2 (cr, baddeleyite,298) = ZrO2 (sol,T) (3) ∆HDS(3) = 20.0 ±0.7 kJ/mol

β-ZrTiO4 (cr,298) =ZrO2 (sol,T) + TiO2 (sol,T) (4) ∆HDS(4) = 60.4 ±5.3 kJ/mol

H(1)298=HDS(2)+HDS(3)-H(DS)4

Hf,ox298= 18.3 ±5.3 kJ/mol

p. 33. Direct reaction calorimetry

Reagents A and B mixed in ratio x/y and placed in crucible are dropped into calorimeter at
temperature Tc (temperature of calorimeter, high enough for the reaction to occur). This is the first
drop.

Q1=H(C,Tc-Tr)+H(A,Tc-Tr)+H(B,Tc-Tr)+fH(AxBy,Tc)

Q1 consists from 3 terms: H(C,Tc-Tr) heat required to heat crucible from room temperature (Tr) to
temperature of calorimeter Tc (enthalpy increment between Tr and Tc). Second and third terms are
heats required to heat pure component A and pure component B from room temperature to
temperature of calorimeter. The fourth term is heat released due to reaction of formation of
compound AxBy from components A and B at temperature of calorimeter Tc. All values refer to actual
masses involved in measurement.

Then sample was then extracted from calorimeter and kept in room temperature thermostat.

The second drop is a drop of crucible with the formed compound kept at room temperature into
calorimeter at temperature Tc. Q2 consists from heat required to heat crucible from temperature Tr to
Tc and heat required to heat compound AxBy from Tr to Tc.

Q2=H(C,Tc-Tr)+H(AxBy,Tc-Tr)


Q1-Q2= H(A,Tc-Tr)+H(B,Tc-Tr)+fH(AxBy,Tc)-H(AxBy,Tc-Tr)
Tc
∆ H ( A , T r−T c )=x A ∫ C P ( A ) dT
Tr

Tc
∆ H ( B ,T r −T c ) =x B∫ C P ( B ) dT
Tr

Tc
∆ H ( A x B y , T r −T c ) =∫ C P ( A x B y ) dT
Tr

Tc
H(AxBy,Tc-Tr)H(A,Tc-Tr)H(B,Tc-Tr)=∫ ∆ ❑C P ( A x B y ) dT
f

Tr
 Tc
Q1-Q2= fH(AxBy,Tc)-∫ ∆ ❑C P ( A x B y ) dT =fH(AxBy,Tr)
f

Tr

The Fig 1 a show the detector response during drop experiment for sample of pure Ag at T c=974 K.
The acquisition system computes the integral of difference between the response curve and
computed baseline. The measured curve presents data in mV, by integration over time we get values
in mV·s. Sensitivity (the energy conversion coefficient in mV/W).) is determined by dropping several
samples of known heat content.
t2
m St ∆ H St =K H ∫ Φdt
t1

Fig. 1 a. For calibration pure metals are dropped Fig. 1b. Curve (a) – first drop Q1. Two effects are
from Tr into calorimeter with Tc. Example is for seen: endothermic is the result of heating from
Ag. The observed effect is heat required to heat Tr to Tc and exothermic is heat of reaction.
Ag from Tr to Tc. Curve (b) – second drop Q2 endothermic effect
is the result of heating from Tr to Tc

Table. Results of measurement for CeAl2

Sample Sample mass (g) Q1 (J) Q2(J) fH(CeAl2)298 (kJ/mol-at)

1 0.9959 -144 +677 -53.3
2 2.0008 -420.6 +1207.6 -52.6

0
(Q ¿ ¿1−Q2) M
∆ H 298 ( Ce Al 2 )= ¿
f m∙ 1000 ∙ n
where M=194.072 (g/mol) molar mass of CeAl2, n=3 – number of atoms in compound CeAl2

p.34.

Combustion bomb calorimetry is used to measure heat of combustion reaction at constant volume in
isolated system. The Cv is heat capacity of calorimeter and sample measured at constant volume.
Calibration should be made using Hcomb of known substance.

Hcomb=Cv·T+RTcombngas

p. 34-36. Partial enthalpy measurements using isoperibolic calorimetry

The area under the heat exchange curve is proportional the heat effect Q1

Δ
 t∞

Q1=W ∫ ∆Tdt
0

Q1=Qdissol+Qheatni, where Qheatni enthalpy of heating of sample from room temperature to experimental
temperature, ni is amount of added substance, Qdissol is heat effect of sample dissolution at
experimental temperature

T
W is the calorimeter constant is determined
t by calibration using any substances which do
 Tdt not react with investigated alloys (e.g.
0 ceramics, tungsten). Qheat is enthalpy
increment known from literature:
heat T
Q =∆ H 298
T
∆ H 298
W=t
∞

∫ ∆ Tdtat the beginning

Sometimes W depends on alloy mass (m) W=a±b·m. Calibration must be performed
t0
and at the end of experiment.

Heat exchange curve related with dissolution of investigated sample in the system with negative
deviations from ideal mixing

Heat exchange curve related with dissolution of investigated sample in the system with positive
deviations from ideal mixing
 T0
∆ H i ( x )=−∆ H 298−∆ H Tr ,i +W ( x ) F ( x )−C pi ∆ T (x)

∆ H ( x )=∑ x i ∆ H i ( x) i=1,2
i

H298T0 is enthalpy of heating from 298 to T0 (T0 is initial temperature of calorimeter at x=0, W –
thermal equivalent of calorimeter, T(x)=T(x)-T0, HTr,i – enthalpy of fusion if T<Tfus,i, CP,i – heat
capacity

H

H B H A

α-function

 H A
H B
A xB B

Gibbs-Duhem equation

(1−x B)d μ A + x B d μB =0
γA ln γB at x B
xB
∫ dlnγ A =ln γ A =− ∫ ( 1−x B )
dln γ B
γ A=1 ln γ B at x B =0

If lnB is obtained experimentally then lngA can be obtained by integration (graphically or

analytical function
 lnB

Integration of the Gibbs-Duhem equation: Method of Darken

ln γ B
Introduction of function α B =
¿¿
xB

ln γ A =−α B x B ( 1−x B ) + ∫ α B d x B
x B =0

∆ HB
In case of partial enthalpy is measured α B = 2
( 1−x B )
xB

∆ H A =−x B ( 1−x B ) α B + ∫ α B d x B
xB =0

Integral enthalpy of mixing is expressed as ∆ H =x A H A + x B H B can be presented as

 xB xB
∆HB
∆ H =( 1−x B ) ∫ α B d x B=( 1−x B ) ∫ 2
d xB
x B =0 x B =0 ( 1−x B )
The function B is usually expressed by polynomial and can be easily integrated. Similar
expressions can be obtained for other excess functions Gex via ex and Sex via Sex

p. 37- 39. Differential scanning calorimetry (DSC)

There are two kinds of DSC – heat flux DSC and power compensating DSC. In heat flux DSC the
sample and crucibles are connected with metallic stripe. The are placed in the same furnace. In case
of power compensating DSC the sample and reference crucibles are in separate furnaces.

Heat flux DSC - measure temperature difference Power compensating DSC – measure power
between sample and reference. Heat flow rate compensation to keep the same temperature in
is proportional to temperature difference both furnaces
Φ r=k (T )∆ T SR (T )

DSC can be used to determine temperature and enthalpy of transformation (reaction).

Enthalpy of transformation is determined by peak integration

t2

Q r =k ( T )∫ ∆ T SR ( T ) dt
t1
Qr is heat of reaction, k(T) is calibration factor (sensitivity), TSR is temperature difference between
sample and reference measured using thermocouple (usually expressed in mV). Calibration using
pure metals, for which enthalpy of melting are very well known
t2

=k (T )∫ ∆ T SR ( T ) dt
melt
mc ∆ H
t1

Calibration factor vs. temperature of melting for pure metals (e.g. Ga 303 K, In 430 K and Sn 505 K)

p. 38-39

Heat capacity measurements using DSC

Three-step method

1. Empty crucible measurement 0(T)

2. Calibration substance measurement
(e.g. synthetic sapphire, Pt)
C P , c mc β= K Φ (T )(Φc −Φ 0 )
K(T) – calibration function,  heating
rate, CP,c is well known from other
measurements
3. Sample measurements
C P , S mS β=K Φ (T )(Φ S−Φ 0 )
All three measurements have to be
performed under exactly the same
conditions
Good thermal contact between sample
and crucible is required
mc ∆ Φ S
C P , S= C
ms ∆ Φ c P , c
S=S-0, c=c-0, - heat
flow rate difference between
substance S / calibration substance Heating rate s, c,  vs. time, t. Temperature-
c and zero-line 0(T), mc-mass of time program: isothermal holding at starting
calibration substance, ms – mass of temperature, heating with constant heating rate 
sample, CP,c –heat capacity of and isothermal holding at end temperature
calibration substance

p.39.

Drop calorimetry (usually inverse)

By dropping samples kept at room temperature into calorimeter at different temperatures we get
dependence of enthalpy increment on temperature.
T
= ∫ C p dT
T
∆H 298
298

By differentiating enthalpy increment the heat capacity is calculated C P = ( ∂∂TH ) P

p. 40.

The Gibbs energy and activity measurements

Vapor pressure data using Knudsen effusion cell

Condensed sample is placed in a Knudsen cell, small enclosure, that is uniformly heated and held
until equilibrium between condensed and vapor phases is attained. The vapor is continuously
sampled by effusion through a small orifice in the cell. A molecular beam is formed from the effusing
vapor and directed into a mass spectrometer for identification and pressure measurement of the
species in the vapor phase.
All classes of materials can be studied and all constituents of the vapor phase can be measured over
a wide range of pressures (~10-4 to 10-11 bar) and temperatures (500-2800 K). The ability to selectively
measure different vapor species makes KCMS (Knudsen effusion cell combined with mass-
spectrometry) a very powerful tool for the measurement of component activities in metallic and
ceramic solutions.
The output of the mass spectrometer is in ion intensity, Ii. For many thermodynamic measurements
this must be converted to partial pressure, Pi, via the following equation:
kT I i
Pi= (1)
σi
Here T is the absolute temperature of the vapor source, σi is the ionization cross section, and k is the
machine constant. The machine constant is a combination of numerous factors involved in the
formation of the molecular beam, the ionization process, ion collection efficiency, transmission
efficiency of the analyzer, and collection efficiency of the detector. To calculate absolute vapor
pressures the values of both k and σi must be known. In order to determine the machine constant, a
number of experimental issues must be addressed.
A number of requirements must be satisfied for precise measurements. The cell material should be
inert. Generally metallic alloys are studied in refractory ceramic cells (Al 2O3, ZrO2, Y2O3 etc.) and
ceramics are studied in refractory metal cells (W, Mo, Ir etc.). The size of the orifice is generally
determined by the maximum vapor pressure over the sample in the temperature range of interest.
Reliable vapor pressure data are available for most pure metals and these are excellent standards.
However, care must be taken to measure the standard and sample vapor pressures under exactly the
same conditions. The vapor pressure of a standard is measured first to obtain the machine constant
then samples are changed and the ion intensities for the alloy are measured. However, for most
instruments, the machine constant changes from run to run.
One of the approaches to solve this problem involves taking the ion intensity ratio in a binary alloy
and manipulating the Gibbs-Duhem equation to cancel the calibration constant. The resultant
equation for an alloy AB is:

ln γA =- ∫xAd[ln(I+ A/I+B) - ln(xA/xB)]

Here γA is the activity coefficient of A, xA and xB are the mole fractions of A and B respectively, and IA
and IB are the measured ion intensities of A(g) and B(g) over the alloy. This technique has been widely
used to obtain activities and partial molar quantities for a number of systems. It requires only
measurements of the alloy—no standards are necessary. The drawback of this technique is the need
for measurable vapor pressures over a range of compositions for both components. An example of
some data for the Fe-Al system at 1300 °C obtained by Jacobson and Mehrota (1993) along with
phase diagram is shown in the figure. Note the negative deviations from ideality, which are
consistent with solution models of this system.

Activity data for the Fe-Al system obtained using Knudsen effusion cell at 1300°C and phase diagram
of the system

p.41

Electrochemical methods (electromotive force EMF measurements)

Chemical reactions can be used to produce electrical energy in voltaic (galvanic) cells. The function of
a voltaic cell is based upon reactions illustrated in equation (1).

Zn(s) Zn2+ (aq) + 2e- (Oxidation)

Cu2+(aq) + 2e- Cu(s) (Reduction)

Zn(s) + Cu2+(aq) Zn2+ (aq) + Cu(s) (Net Reaction) (1)

Oxidation occurs on anode and reduction on cathode. A salt bridge must be used to avoid
polarization of the electrodes by facilitating the circulation of ions from both cell compartments. The
cell voltage, or the electromotive force (abbreviated emf), is indicated on the voltmeter in Volts. In
general, the emf of a voltaic cell depends upon the substances that make up the cell as well as on
their concentrations. Hence, it is common practice to compare standard cell potentials, symbolized
o
by E cell. These potentials correspond to cell voltages under standard state conditions - gases at 1
o
atm pressure, solutions at 1 M concentration, and temperature at 25 C.
Just as the overall cell reaction may be regarded as the sum of two half-reactions the overall cell emf
can be thought of as the sum of two half-cell potentials, that is, the sum of the voltage of the
o o
oxidation half-reaction (E (ox)) and the voltage of the reduction half-reaction (E (red))
0 0 0
Ecell =E(ox)+ E(red) (2)

Because it is impossible to measure directly the potential of an isolated half-cell, the standard
hydrogen half-reaction has been selected as a reference and has been assigned a standard reduction
potential of exactly 0.000 V;
0
+¿+2 e= H 2(1 atm) (Ered =0)¿
2 H (1 M ) (3)

The complete notation scheme for a galvanic cell is written with the anode on the left and a double
vertical line denoting the presence of a porous plate or salt bridge.
2+ 2+
Zn | Zn || Cu | Cu. (4)

o
The sign of ∆E cell is positive for a spontaneous reaction and negative for non-spontaneous reaction.

The Nernst equation is:

0 RT
∆ E cell=∆ Ecell− lnQ (5)
nF
where F is Faraday constant, R the universal gas constant, n the number of electrons transferred, and
Q is the reaction quotient.

For a general reaction or process of A and B giving products C and D:

aA + bB → cC + dD (6)

the reaction quotient, Q, is:

[ C ]c [ D]d
Q= a b (7)
[ A ] [B ]

The ∆G of a process at any concentration of A, B, C, and D, is given by:

0
∆ G=∆ G + RTlnQ (8)

The cell potential of a redox process is related to the Gibbs energy change as follows:
0 0
∆ G =−nF E (9)

In this equation, F is Faraday’s constant, the electrical charge on 1 mol of electron 1F = 96,500 C/mol
= 96,500 J/V-mol and n represents the number of moles of electrons transferred in the reaction.
Examples
E.M.F measurements using galvanic cell
Zn(liq,pure)‫׀‬ZnCl2 in (LiCl-KCl) ‫׀‬Zn-Pb(liq)
The value of emf measured between zinc and 6 alloys as function of temperature is shown on the
figure 1.
Fig. 1. Change of EMF with temperature

Fig. 2. The activities of both components in liquid Zn-Pb alloys

The activities of Zn were calculated using equation

RTlnaZn=-nEF
Based on these activities of zinc, the activities of lead were calculated using the Gibbs-Duhem
equation.
Calculated activities of Zn and Pb are shown in Figure 2.
Table. Experimental results of liquid Zn-Pb alloys at 1050°C
Sample No. NZn E at 1050°C E/T (V/deg) aZn (at 1050°C)
1 0.1 65.38·10-3 0.112·10-3 0.314
2 0.25 30.30 ·10-3 0.068·10-3 0.587
3 0.4 16.87·10-3 0.046·10-3 0.743
4 0.55 10.85·10-3 0.033·10-3 0.826
5 0.7 7.37·10-3 0.021·10-3 0.878
6 0.9 3.72·10-3 0.07·10-3 0.937
p. 37.
Thermodynamic data for redox reaction Cu/Cu2O
Electrochemical cell consists from two electrodes A and B each defining chemical potential of oxygen,
μOA and μOB separated by the oxygen-conducting solid electrolyte calcia-stabilized zirconia (CSZ).
2 2

Under ideal conditions the open-circuit emf, E, developed in such cell is related to the difference in
μO between the two electrodes
2

B A
4 FE=μO −μ O 2 2

A=sample, B=ref

Then for reaction 4Cu+O2=2Cu2O

❑ ❑
−4 EF=μ O (sample) −μO (ref)
2 2

Cu+Cu2O O2(± 62) = -347705+246.096T-12.9053TlnT (750-1330 K)

0f
The above presented equation for O2 is RTln PO =2 Δ r G❑ (T). The value of rG0f at 1000 K is equal
2

to -95.378 kJ/mol is in a good agreement value -95.507 kJ/mol from the reference thermodynamic
tables of I. Barin (1995, Thermochemical data for pure substances).

The Gibbs energy data can be analyzed to derive standard enthalpy of formation at 298.15 K
T
∆r H
0
m ,298.15 =∆r G
0
m ,T − ∫ 0
∆ r C P ,m dT + T ¿ ¿
298.15

The value H0f298.15 obtained from analysis of electrochemical data -170.508 kJ/mol is in perfect
agreement with value from tables of I. Barin (1995) equal to -170.707 kJ/mol. This is so called Third
law analysis to calculate rH0298.15 from experimental rG0T using calorimetric data on rS0298.15 and
temperature dependence of rCP.

Second law analysis:

0
∆ r GT =∆r GT + RTln K P
KP is constant of the reaction at temperature T. Constant of the reaction is temperature dependent.
0
In equilibrium DrGT=0. Differentiating on T ∆ r GT =−RTln K P

( ) ( )
0
∂ ∆ r GT ∂ ln K P
=−Rln K P−RT
∂T P ∂T P

( ) [ ( )] [ ( )]
0 0 0 0
∂ ln K P 1 ∆r G T ∂ ∆ r G T 1 ∆r G T 1 ∂ ∆ r G T 1
= − = − =
0
∆ HT
2 r
∂ T P RT T ∂T P T T2 T ∂T P RT

Integration expression ( ∂ ln∂ TK ) = R1T ∆ H

P

P
2 r
0
T results in

( )
K P (T 2 ) ∆r H T 1 1
ln = −
K P (T 1 ) R T1 T2

lnKP
 1/T
If rCP is known rH T can be recalculated to T=298.15 K.
0