Differential Scanning Calorimetry(DSC)

The device is a thermal analysis instrument that determines the

temperature and heat flow associated with material transitions as a
function of time and temperature.
(OR)

DSC is thermodynamical tool for direct assessment of the heat energy

uptake, which occurs in a sample within a regulated increase or decrease
in temperature.
Based on mechanism of operation

1. Heat-flux DSCs
2.Power compensated DSCs
𝑞 = ∆𝑇/𝑅
Instrumentation of DSC / Block Diagram
DSC curves Interpretations
Applications of DSC

 Purity determination

 quantitative measurements

 polymer analysis

 Drug Analysis

 Oxidative stability
 Purity determination

 Impure compounds will exhibit a broadened m.p. dip that begins at lower
temp than a pure compound.
 it can be used in determination of purity of the different compounds.

2
𝑅𝑇0 𝑥 1
𝑇𝑠 = 𝑇0 −
∆𝐻𝑓 𝑓
Where, 𝑇𝑠 is sample m. p
𝑇0 is theoritical m. p. of pure compounds.
R is the gas constant(8.314 J 𝑚𝑜𝑙−1 𝐾 −1 )
X is mole fraction of impurity
f is the fraction of sample melted at 𝑇𝑠
∆𝐻𝑓 is the heat of fusion of pure major component (𝐽 𝑚𝑜𝑙 )

𝑅𝑇02 𝑥
 A plot of 𝑇𝑠 against 1
𝑓
gives a straight line of intercept 𝑇0 and slope
∆𝐻𝑓
may be obtained from the DSC scan, allowing x to be calculated
 quantitative measurements

 DSC is preferred for quantitative measurements

 This is because it requires only standard for peak area calibration as K is
independent of temperature
 K is determined from standard of high purity with an accurately known
enthalpy of fusion. Pure Indium with m.p. 429.5 K is used for this purpose
 Modern instrument under microprocessor control will evaluate K using the
peak area obtained from the melting endotherm of indium.

𝐴 = ± ∆𝐻𝑚𝐾
 Drug Analysis

 In pharmaceutical industry it is necessary to have well-characterized drug

compounds in order to define processing parameters.
 For instant, if it necessary to deliver a drug in amorphous form.
 It is desirable to process the drug at temp below which crystallization can
occurs.

 Oxidative stability
 To study the stability to oxidation of sample generally requires an airtight
sample chamber.
 Usually, such test are done isothermally (at constant temperature) by
changing the atmosphere of sample.
 Such analysis can be used to determine the stability and optimum storage
condition for material.
 polymer analysis

 DSC is used widely for examining polymers to check their composition,

such as percentage of Crystallinity.
Heat put on polymer melts = 𝑯𝒎
Heat absorbed by the heater during the crystallization = 𝑯𝒄
𝑯𝒎 - 𝑯𝒄 = 𝑯′
(𝐻′ is the heat absorbed by that part of the polymer which was already in the
crystalline state before we heated the polymer above the 𝑇𝑐 )

𝑯′ 𝑱
= = g ………(𝒎𝒄 )
𝑯,𝒎 𝑱 𝒈
,
(𝑯𝒎 is the specific heat of melting)
 This is the total amount of grams of polymers that were crystalline below 𝑇𝑐
 Dividing this by the weight of sample ( 𝒎𝒕𝒐𝒕𝒂𝒍 ), we get the fraction of
sample that was crystalline and then of course the percentage of Crystallinity.
 𝒎𝒄
= 𝑪𝒓𝒚𝒔𝒕𝒂𝒍𝒍𝒊𝒏𝒆 𝒇𝒓𝒂𝒄𝒕𝒊𝒐𝒏
𝒎𝒕𝒐𝒕𝒂𝒍

Crystalline percentage = 𝑪𝒓𝒚𝒔𝒕𝒂𝒍𝒍𝒊𝒏𝒆 𝒇𝒓𝒂𝒄𝒕𝒊𝒐𝒏 × 𝟏𝟎𝟎

 Advantages of DSC

 Simple and rapid procedure of analysis , typically 15 to 30 min per

determination.
 Ideal for comparison of sample purity for example in quality control.
 No need to calibrate over entire temperature. (K is temperature independent)
 A more specific application of DSC where DTA cannot be employed in the
detection of magnetic transition in the materials. The magnetic transition with
∆𝐻 = 0 but with the maximum heat capacity at the transition temperature.
 Thermometric Titration
 basic principle of thermometric titrations is based on the change in temperature
with the addition of titrant and determine the end point from a plot of
temperature vs. volume of titrant.

 The titrant is added to an isothermal titrate in an adiabatic titration calorimeter.

In most instances there occurs a change in enthalpy concomitantly, yielding a
corresponding heat of reaction. As a result these are also called enthalpy
titrations and the titration curves are called enthalpograms.

 It can be exothermic or endothermic.

 In thermometric titration, change in temperature occurs only when titration is in

progress and sample reactant is present. Thus, start and end point of a titration
are readily observed and the number of moles titrated is calculated as in regular
titration.
 Theory
 In ordered to carry out a thermometric titration , the essential condition is that
there should be change in free energy in the end point region.

 As changes in free energy is related to enthalpy change (∆𝐻 = ∆𝐺 + 𝑇∆𝑆). It

means that a thermometric titration is only feasible when there occurs a
significant enthalpy change in the end point region.

𝐊. ∆𝐓
∆𝐇 =
𝐍

∆𝑯 is in Kcal per mole

∆𝑻 is change in temp corresponding to the formation of N moles of product
K is the apparatus constant and is equal to the effective heat capacity of the titration cell
plus reactant solution.
 Typical shapes of enthalpogram

 The AB is a trace of the

temperature of the solution
before the addition of titrant. If
D the AB shows a marked slope ., it
Temperature

is an indication of excessive heat

C
B’ transfer between the solution and
its surrounding.
 At B, addition of titrant begins
ΔT  Line BC shows, the gradual
evolution of heat of reaction.
 The point C is the end point.
A B E  The line CD slope either up or
ΔV down
 The linear portions of the curves
are extrapolated to give the
Volume of titrant initial and equivalent point.
Typical Enthalpogram for exothermic reaction and endothermic reaction

exothermic reaction

endothermic reaction
 Both cases the excess reagent branches of the enthalpograms (CD) are drawn
with ascending slope because the dilution of most titrants is an exothermic
process.

 In order to minimize variations in heat capacity during titration, it is customary

to use titrants 50-100 times more concentrated than the unknown titrated. Thus
the volume of titrate solution is maintained virtually constant, but the titrants
are diluted appreciably.

 The heat of dilution can be corrected for conveniently by the linear back
extrapolation CB´.

 Under these conditions, the extrapolated ordinate height BB´ represents a

measure of the change of temperature. T, due to the titration reaction, as well as
of integral heat, Q, evolved or absorbed viz.,

BB´ α ΔT

𝐍. ∆𝑯
∆𝐓 =
𝑲
Instrumentation
 A motor driven automated burette contained in a thermostated
water jacket so that the temp. of the titrant remain constant to
273.21 K.

 An adiabatic titration chamber such as a Dewar flask or

insulated beaker closed with a stopper provided with holes for a
motor driven stirrer, a thermistor, for burette tip.

 A thermistor bridge assembly for measuring the temperature

changes in the solution.

 A recorder which plots the potential change.

 Procedure
 A known volume of the solution to be titrated is taken in titrating vessel and
thermistor is connected to one are of Wheatstone bridge.

 The titrant is filled in the burette, the concentration of which is generally kept
10-100 times more than that of titrating solution in order to avoid the volume
correction and to minimize the temperature variation between titrant and the
solution

 The titrant delivered automatically to solution at constant rate (0.5 cm. Cube
per min < 3 cm. cube per min)

 The reactant are thoroughly stirred with a motor driven stirrer.

 The heat liberated or absorbed in the reaction unbalance the bridge potential
which is plotted by the recorder.

 Unbalanced potential of 15.7 mV corresponds to change of 274 K ( 1 degree

Celsius).
Thermometric Titration Application
 Heat of the reaction is most general property of chemical processes,
thermometric titrations have a wide range of applicability in quantitative
analysis.

 It includes the determination of the concentration of the an unknown

substance, the reaction stoichiometry, equilibrium constant and the
thermodynamic quantities G, H and S.

 These have been applied successfully to all types of titration processes

including acid-base (neutralization) reactions, redox reactions,
precipitation reactions, and complexometric reactions in media ranging
from aqueous at room temperature to molten salt at 350°C.

 Lowest limit of concentration that can be successfully titrated in 10-4 M.

 It is non-specific (limitations)
 The classic example of thermometric titration is in titration of boric acid (Ka
= 6.4 x 10-10) with a strong base ( such as NAOH) which is otherwise very
difficult to perform
 TT process extraordinary potentiality for determining heat of reaction in a
dilute solution rapidly and conveniently.
 Analysis of mixtures is possible when two species have different
equilibrium constants and heats of reaction with the titrant. For example,
in the titration of mixture of calcium and magnesium with EDTA. Calcium
(Kf = 10 11) reacts first and exothermally (H = -5.7 Kcal/ mole) and then
magnesium (Kf =10 9.1) reacts endothermally (H = 5.5 Kcal/mole).
 Precipitation and ion recombination reactions by TT also yield good
results. For example , halide reacts with silver or mercury (II) and cations
such as Mn(II) with EDTA and oxalate. Titration of silver with halide can be
carried out at elevated temperature in molten state.
 To determine equilibrium constant of complex formation by
thermometric titration. Let us consider
Where equilibrium concentration [A] and [B] can be calculated using analytical
concentration (A) and (B) . Thus we have

These concentration are then used to calculate equilibrium constant (K) using
the expression.
 Consider the reaction between a metal (M) with a ligand (L) to form a complex
ML. Initial concentrations for both are given to be 0.015 M. It gives an
enthalpogram similar to above shown figure, where h and ht were measured to
be 58.2 and 67.9 °C respectively wherefrom stability constant of the complex
can be estimated.


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