isotherm

124
(i) static or weight
avimetry,
Thereoare, in fact, three types of thermogr the sample
in
since long ofincreas-
series
(i) in a
constant tcmpcra each step
is recorded as a function of time at aog weight at the
to cons unfortunately
In quasistatic TGA thc samplc is heated
uniform rate, but convection, the
ing tempqr@turcs.: a and
is heated at alr [uoyancy often
Overlooked.
(iil) In dynamic thermogravimetry the samp
quantitative
constants.
of precise ofa'utomatic
it is, determination advcnt
used' the the
behaviour and cannot in 1923 with
bclan only recently
recording TGA instruments,
ofreprodgc-
01.3 -INSTRUMENTATION
at which thermobalance.
In analysis;the soÆålléé
ible and recognisable stoilhiomeuy is produced il
by the use oftfie instrumental te-
buf the
There are several available cOinme/ciailY, 'h&hécontrol
temperature anti
quirements in TGA are a precision balance. heåting device,
devices.

Furnace
O O) Co•ntrbller

- Furnace
X-Y Récorder.
SampleCup
.vacuuaw

Gas •

BalaaceControi

8alatce

. AscnehiåE&modern •themötgraüiiiiet?ic-analysCi.•
9) mechanism 'if TGA 'tn'ay be a' üfod?fi-
l t
caådh ofå$inghé•o? %ålancé, ånseléct+oniéå11Y
Séif-bålaiiéirig device, a tdrsion
Siii+i4,Spgng dépéndiig•åpön the:reqmrélifeiit} 'For thé p*éliminary
'work in 'tiiölabdiåtöry, a' gegisiåp •törsionbalalicelmay easily hdopted fof use as a
•thermovalåncé.•
aractenstics :
(a) should be sirffpde
(b) At should hayé'
(c) Should belableåoåe$pond råpidIy•t0ÆhångéSin veight and*
(d) It should be ru2ged, accurate, very sensitive and mechanically stable.
å>tmogravimetric Analysis 125
Almost all the thermobalances that have been used areeither the null point o? the' deflection types
In some modem commercial ,instrument$,abeam of,light obstructed by a wave
GiÅchqd to the end of a quanz. spring has been-used in quartz.spr.ing balance: Photoelectric detection
used case: Severai commercial thennobalances use torque motor-a galvanometer with the'
to the needle to some null-point. Nutl is detected by a pair of split photocells behind
in a iight beam.
(it) lieating and temperature men«urement : The furnace design and control have taken
various foans depending on the degree of sophistication of the instrument. The main re-
uirement is that the heatin rate be smOothpso that it can tnåintainteither a
ro oramme 100-500 0C per hr.) ora txed tem 'erature. The simp cst temperatur programme
is a variabie trans onner. t er equipments use conventiooal thermocouples or resistance
thennometers situated as close .to the /ümace winding as possible„ Platinum and tungsten
are corntnonl used, the nich ome windings permit a maximurn tem erature of
o
I löo c•, Pt-Rh,up a ast one commercta nstrument is:ca a e of reac in
0
about 1600 C. n One of the most common programmes for serious Ognal from a
the furnace is compared éléctronically against a referenCé poiéf)tiål which
can be programtned to correspond no a variety of heating modes and heatingratey.
The size 9fthe fymace is qi$O 3tna!1 furnace coor" Very Qü!Cklyand it is
difficult tb contiol lineÅrheating rate. Although IArgefurnaces maintåin•isothe.rmatempera-
ture and are suitable to maintain linear heating fate, but •they.again th9 Féquirgdgemperature
very •late.
Cone of the most important and also difficult problems in TGA is the measurement of sample
temperature)As has been discuSséd:below,the self-heating during oxidation, _tbegaseous
pioducts produced during 'heatingand the ruction ofthe sample witfrih%frnogphere e
some of the important problems which introduce error*n tem rature,meay_ement The
usual rate o? heating per minute.
s:ample cups•: SeVerål Shape-sofs4mple gu'P9hå'v;gbeeh'uSed foiTGÅ 'work depending
on: the- iiature of 'Ithé' syStem_ ei enerally'theré år&foui bas:c e)
-s cups-s al ow pan, deep crucible, covered cup and retort cup.
"Shallow • an; ar&used when volatile products'afrepfådücéd 'dåting'heatin a'n'dit is nec
Sary thé gäSes to" 1 se to t e stirface to•eScaPe. eSe Fans •håvs::fölinrfi
.appIca ton e yo t et e ofpolymetS.„
Deep ere•used in. induétria!sé21e calcinatiops o? surface. pr_ea
overed cu s are used where -the.studies have.to.be carried out;in self-oer o-
sphere:
R to t cu s.ar u inboiiin ointstudies.
: Atmosphg?econtrol isiextremely important TOA because the
in,thé.sampletts up to the gaseouspr _us. orme samp e atino or
_eyeac io o a, m e with the* a an e control-of atmosphere cen be.
v.öacbigyedeigh#QiQ the e a puce:rln kinds of kineticstudies w ere ts
necessary to carry out t e e n g samplf,geoeqae -a o p ereoulation is
ectg e samp e contatneqwlt pose Itt1Qglid—anothei way
the q os 'di_.l.ng g w o e a
_¯tr•, r on,carbon xi e h dr genor BecauspOfthe IOC!thærrnalcondus-.
Alt%'jty'aqéyepy low d the study
d e stud of io trof ey r I thei I gsofc{fnz
pounds.. IQall serious works, it is necessary to regulate the gas pressure.
 126 Chemical Analysis
11.4 DERIVATIVE
THERMOGRAVIMETRICANALYSiS (DTGA)
Several commercial thcrmobalanccs are provided with electronic circuits to record 'the deriVA.
tive automatically.
As in thermogravimetry,the derivative thermo ravimetric analysis involves the•s
measurementrf the ra g.of weight o the specimemas it is heated at a um
ara e. n or er to appreciate the usefulness of derivative theimogt•aVimetricanalysis, let•uS ékamine
curves obtained in the pyrolysis of a mixture containing calciutn carbonate and magnesium carbonate
(see Fig. I .2). It is evident Tromthe figure that the plateau in the at 7000Cis'
quite clear, but the shoulder at about 870T is not very clear. However, in the thennogram obtained
in DTGA, the shoulder has been clearly resolved into a peak. ' It could riot have been pin-pointed
without derivative curve.

MgC03
VGA
Ngo +
caug (003)?
"go + 30
40
Ngo
-50
400 600 800 1000
Temperature IOC
•Fig.:' •Relatipn between TGA and D_TGcurves for thF pyrplysiSpf CaC03 •and.MgCOJ.
'FACTORS AFÉECfiNG TGÄ
In addition to the obvious sour9e; oferr,ors, sufh as sensitivity octhe balance, errors inveighing,
unusuål difficulties inhereht in a cheÆical s)'Stem; eic.,•"the followmg fagt01ismay affeci the
accuracy
of IGA resÜlts
I. Effect of Changing Air Buoyancy and Convection : The most favpured arrangement foi
thermöbalance is to suppoh the ingrt sample from *below.in the centre orp cylind!ical, capped tube'
turnace- Cinder this cOndiiiunthé samp}egnay:shqw aa.qpparen! veigi•t te
correction häs, therefore, to applied to the récord$d weight chånge. The causes for the apparen%
gazn are : decreased buoyancy, conVection •andthé•effect of heat of balance,
mechanism. The -magnitüde'ofthe appareilt weight gain •måy be feduced considerably by proper
venting but for careful work correction has to be used
2. Measurement of Temperature : The uSüa!pråeticeih TGA1sto likasvre the temperature
in the -furnaée:nearthesampJe;-thetemperatutes lso determined are u'ually-•higheithaiiithose deter-€
urÆr,edby measuring thé temperature-directly: TheÆåuSe;ofthis differ3{
ence is partly due theme! lagand partiy_düdtothe-finite time scaüse'd9et±table
change
in weight. ' The results Of€ariåus•Workerssåggest that when thetü@obäiåiéé'is used tö süidythedryin$
of bulky precipitates„itsvouid bé well to use'slow rates of heating.
3. Effect of Atmosphere?' When åsamp!eis dried or decomposed in thermobalanee in
ent zir, thé atmosphe?g near•thgéampté is' CominUot1Flymodified ddb to *théi'ååditibfi lof gaseous-.
decomposition produdfs ofåiigilial gaéL y feaciiön hwitllihé 'samplél Even small
changés in compo'åitioiofihiéaåiiosbhgie cah a'fiict ihetmogråljv. it' is thétefore 'tiécessary to
flush the "thermobalånce coniinuoåslV With gasliriorder '{0 rhailitåih åé'Cötßtant ah åtmosphere as
possible.
 will tend to compensate
$å+,peraturewill be additive. But when ihe reaction is exothermic this effect
cabh other.
the thermogram apprecia-
'Effect of Ileating Rate : Heating rate has been found to affect
u•ed for kinetic analysis. Fig.
$19!The effect of heating rate is important if the thermogram is to be
oxalate monohydrate. .The
413.Gliustrates the effect of heating rate on the thermogram of calcium
The loss of CO com-
from the room temperature to i000C corresponds to monohydrate.
1.3. that the three reactions-
mences at 4 1.30C and thåhof OX),at 6850C. It is apparent from Fig. 1
onset and decomposition
dehydration, loss of CO and loss of O/ at lower heating rates have lower
teriF&atures.
mg so .'0%20

Stan At 3ÖooC/hr
Afl 500C(hr corrected for
330360 differences in seale and
apparent weight gain
970
Sts!
485

Fig. 11.3. Effect of heating rat; on the,thermogram of CaC20a.V%O.

Similarly, on heating isl(S04 71420at 2.50C(t11jns only one platyex the TG,curve corresponding
is obtained, but if it is heated at therate of0.6)0C/min. the curve breaks corresponding
to NiS04,6H20, NiS04. 51420,NiSO. 41420, NiS04. 31420, NiS04, 2H20 and NiS04. H20 are ob-
}$iP9d.
Sampl? Characteristics
(G) %'eightof the Sample : A large sample•affectsthe T.G. cuae and the
linearity as the temperaturerises. hénce, small samples are preferred. If 20 mg. of the
'CuÜ04. 5HiO is used, 7±2Yuexcorresponding toCuS0413 H20ts obta:nea, It-only u.)
mg of the samp!e is used this plateap can be obserVed.
(b) Pårticle Size • Pariicle size also a
iower temptrature while largeq size particles 'f the såmple take longér time and decdmpose
eat
g;ompactness oft&€ Sgmple.: -Compact.;amplg$ decompose'at higher temperaafre than ihe
n190'sesamplgs
Thésoufée and ethod of preparation Ofthe sample also
have•been föund to affect TG curve: For exampl precipitafed at a
differeng temperature than,the naturallyoccurring g(OHh.
APPLICAtlOÅOFTGA
fl. of Drying Tempgraty:re kange : Themogravimetric analysis is
widely used in qualitative aud quantita}ive and ihéimai Stability s;Gdiés -etc.' {ductrof
Vork in thermogiåyiqytry has been done•tp *tablish Optimum temperature rengés for the cotuii-
•tioning of precipitates for Conventional gravimetric analysis. Some themogravimetric curves •pre
 Chemical AnalySie
128
ofcalcium oxalate: It is nonnatly•precipitated
shown in Fig. I I .4. Curve A shows thethemogram respectively,td
several platuex corresponding
the monohydrate from hot solution. The curve exhibits room'temperature to Il
000C, anhydrous.*
monohydrate from caleiumcarbonatefro
2260 to 3980C,
39B calcium oxalate from oxide fromqbove 8400C.,
The
6359Cand calcium
460? to if heated to
carbonate is an evcellent weighing fom
a 78 63S calcium the thermo-
.CuqveI) of.Fige 11 4. represents
838 500 2.50C.
oxalate which reveals that dihydrate i;
226 MgC20a gram for magnésium exists between
aphydrpus compound
stablg up to 1600C :
478
and the oxi4e is stable frotp d800C t9
2200 and 4000C
A92Cr0a made as the oxide at
Weighing,therefore, is best
92 , 612 0
tempeéature abpy.e 4}0 C.
S? 256 the T.G. curve of silver
Hg2Ct04 The curve C of Fig. 11.4 represents the excess
chromate. The initial drop in weightlindicat$s
107 bééonhes'.cönstaht anå
water, and just about 920C the weight
yhich oxygen' is lost. The
370
Phos ho-
475 - Molybdate remains so up to 8120 C after
tiwrefore, be repre:.
Temper.ature VEC.
decomposition of silver chromate can,
Fig.' .4.lÆüffifr1es%ötCurve sented as
2Ag2Cr04 + 2Ag + 202.
Silver chromate is thus stable over a temperatuverange of about 900 to 8000C. Hence tn aravi-
metric analysis of chromium, the •préöflt:atéofsilver.chromate can be dried anywhere in this regionl
and, in fact, laboratory manuals direct 10weight the precipitate exactly at 1350C. The initial drop im
weight in curve D of Fio. 11.4 represents the excess water. It is obvious from this curve that mercu-
rous chromate is Ståt)lé over the range 52—2560C,so that this form would be employed for
At 2560C it commenees todecompose int6 Hg20 and the weight becomes constant at about 67 IOC
A
Thus, while ranges of pre-

cipita:e for •laboratory gravime!ric work; thiSIShOuldalwaysbé bornetin Conditions o!

•the pretipitåtiosn• oftenåå#é 'dérofoünd effect ot+théfpyrolYSig-•eårüé:
:Itsi6uld'åiWays bé VrefCrred ty
t
employ- a Slowheating raté.
2. Analysis of Mixtures : An inspection of Fig. 11.4,curves A and B will reveal a significant
difference in behaviour between the 03'alatesof calcium gnd mayi'ésiiiåi•åéiéprés'eiitédby their de,
coraoosizion,reactionsly thät.xnagnesium.mælate!

4790 100 Mgt) C02

mg. i
d e; n .æs_thiöågh éayböåateSta'
•in their {henna!' behaéioÜr permits tiielrqitnu)iaheous dk
1510 6080 tennination by TGA. They tän detenninéd in-amixtui
2
cuüÆ03j2'
by' igiiititig-at two températ täree 500 QC at Which CaCC
and MgO ire stable, while at 900öC.bOih exist
f
simple oxidCS. The wei'éhtéOta mixedFécipitme at the!
3 Mixture two temperatures will peflhit cålculåtion of both the
4000 cium end !nagnesiuni contents of the original Sample.
TGA of Cu-Ag pn dye rglatiygstabi
7000
ties of their nitrates. C. Duval has simultaneouily
ninéd tlié eu 'c!hd thVallöy•6y TGA. TG
Fib. 11.5. fGA aiialy;is of a binary, curves in 'Fig. '11•.5,inäicåté'thal:AgN03 is ståb!e'up
Cu alloy
473 00 after wliich it"lÆek'N02 aud '02 aiki ihé wéigh't t
Tk%ogtavirnetric Analysis
129
comes constant above 608 0C when itis.converted into me-
tallic Ag- Cupric nitrate, on the other hand, decomposes into
steps; CuObeiag stable above 700DC. Thus the
weights ofthe mixed at 400 0Nil! pénnit the analy-
sis of the Cu-Ag alloy.
An inspection of curve of Fig. Il .6 reveals ihe TGA curve
for anhydrous The decomposition pattern is sharp
and ensues at •about 4700 C. The theoretical weight loss for
A bythe reaction
202
for t.0f14 sainplé Of LiC104 is 0.608 g/åm. The
somewhat highef experimental weight loss of 0.625 gram
may be drie to two'fåctOiS'
' '1000 800 600 400 200 0 100 200
(i) possible o'fsåmplé by cdriy-offduring the
Weighloss mg Gain
vigorousdecomposition reactions;and
'11.6. Representative TGA curve.
(ii) the occurrence of{anotherdecompositionre-
(.Å?eLiC104 sample wå. 14 g, ob- ection, 9uch-as
AE-CedW€ight losses by"TGÄ, 0.625
2 Li20 + + 702
loss by analytical balance 0.623'g.•
(28.3 wt-%) + The alkalinity of the decomposition residues obtained at-
f*äÖ4.3H20• (il .7 wt.%). Sample wat tests to the pqesence of Li20.
-0423 g-.observed total wt. loss; by TGA An interesting extension of TGA to rapid quantitative or
0717 g ; by analylical båiaiice 01942 semi-quantitative analytiéa! work is illåStfated b}' the deter-
-étéj%åxtüre of •wt.%),wåfef minat16h of Å*ratgrih tLiClÖ4.3H20åhd LiClOÅ.H)O as-rep-
•regeht'éd%h (Fig? 'it .'6). fi}éVåHpÄé cbmünencéd
0.9985 g; ,ob$€ved. wi, -loss lose water at about 80 0C and attaingd constant weight at about
sy;TGA 0.533: g. and bal- 50 0C Yield molten Lic.-104•.••• lafief started
decomposing rapidly about 470 0 to give såbstantialijLiCl•.
Tae TGA curve B gives vålués•oÉ26.6 'Weightyo watéi ånd 73.4 weight % LiCi04. (as against 28.3
Water' and -71.1 % LiC•104'détem%irfed gtävimétric• iiÉthed)
Ctlrve C TGA run grahvsamplé'åf gross coifipökition 54.i
LiCj04, 2 i:' 0/0" :and 24.6 v.å. % LiCl.: 'Oh thé basis Of weight lbssesdetermined from
dui thé dehydratier. decomposition stépk,•the CompöSition found byfhe TGA was
% LiCiOÜ%19.5 H20 %Lici.
•3. 'Kineti gan•tvused to.tudy
'kinetics of a chemical reaction and to determine basic kineticconstants such as the rate eorß'tant,k,
ziivation energy, E, order of reaction, x and frequ%eåéyfaetor,A. In these methods, a change in some
propyrty (weight, enthalpy, *ength or4 a function of temperatureis measured
-zontinuously and automatically. The following types of reactions inyolving change in weight niay be
34tseßto stud?' reac4ion Fnetic,s :
f.- A (éolid phåse) -4 B (solid phase) (gås phåse)
2. A (solid or liquid phase) [3(gas phasy)
{4(spyg phøye,)+ Bo(gasptya?e)-4 ph9F)
4. A (solid phase) + B (solid phase) C (solid phase) + D (gas phase)
There are two approach* for kinetic htud)gsi, involves t
or $1.at,icme!hod.uvvhich
of the degree of a! gmstan{ (empero(ure•as!gfyt•qtion of time an! t e
-djnarhic method whidh involves the determination of degree' of transformation' co'afunctien of tithe
On
during a linear increase of temperature. Kinetic studies Of the above reactions b} TGA are based
130
Chemical Analysi{

the Arrhenius equation

-ERT

_where Kisthö-råt&öT€eaetion. Eis-thecnergy-of activation, R is the gas

constant and T is the temperature'.
A.Brodio (1969) has developed a method first order reactions. The weight loss y is given
it .(11.2)

end ,ofthe
is the intial sample weight, U', is the weight at time Ortemperature t, and Wooat the
they—axis
process under study. If the reaction is a first order and the error is avoided aspiot of i/yas
and the
versus 1000/T (where Tin 0 K is the temperatUre a! weight loss) should yield a 'straight line.
energy of activation—Ewould be times the slope of the line.
epergy. E, can
Graphical methods for the detennjnation pc Orderof reactionF and the activation
6e obtained by aoother equation(l I .3) •.Æ'Å.C.

E2:30 RAT N log (öW/öT)

A logw log Wr.
weight
where R is the gas constant, T the absolute temperaturemd Wr = (W —W,)Whére W,is the
loss at time tand is the weight loss at the end of the process. From a.plot "f,
...(11.4)
A log wr Alog wr
it is possible to evaluate both E ahdx. The method is somewhat,cumberspme.
Several other methods have bgep proposed to eyalua!é E and The easiest method is isothermal
TGA -in which the sample is paßidly •heated,$qa predetennined temperature and -the "eight loss is
recorded as a function oftime. from seye.ra!such plots at differenttemperatures,the s!opes are
obtained and plotted as a function of weigh; percentage of sample volatilized.: The log of the rate .öf;
the region of .interest is ethenplotted as a (unction of ghe reciprocal temperature for that curve; the
slope of which would be.—2.303E/R. Thef may_nowbe readily calculated.
gases:s.Obvjously
4. Surfact Area Measurerhent : 4t isvellknown:that solidsurfa_cgs.adsqgb
the gas adsorbed on the solid suqfgcewill,contributeito -itsweight. TGA canbe applied to determine
the nitrooen alid other,gases.0 in a conve@tionalmethods a cleaned sailiple suafaye is lhegmostated at
darted temperature in a thermöbalance and a gas at the knowa td te.adsorbed
sice'.'i)' "'+ght gain with time is recoqded, After the equilibriuié%. •Gt..
pressure can be. incqeaseé to oext_desired level. This method has begn used obtain
adsorption isothérrnOf SF
QUESTIONS
l. How many thefmoåpalytihl iTiet$)bds•
do you know)? •Whal the importahéé ofn
ihehnoaqålytical methÖds•?
•What is thermogravimetric analysis ? Discuss the instrument üséd •in ithéånOgfåvimetiic+
analysis.
3. Discuss the factors affecting thermogravimbtric analysis-
4. What is derivåtive thermograVimetrican'alyeiS? is it 'thérmOgravimetric%4
analysis ?
5. Write a note on thé
Whåt is thérmbgfaüinietflöanalysiö? What infoi-måtionscan be obtained from the pyrolyi?2
siScurves ?