Pell de 2 Analytical Methods in Chemistry Spectrochemical Methods + M. USAIAN At [Me OSIRAAIN » [FONT Introduction Interaction of Radiation with Matter Development of Analytical Techniques Classification of Spectrochemical Techniques @) Flame Emission Atomic Absorption Tob (iii) Spectrophotometry (iv) ULV. Spectroscopy DT A () LR. Spectroscopy. «+ wi) N.M.R. Spectroscopy _ Dp T De Electro analytical Methods Introduction“ DSS Gee (i) Potentiometzy Gi) Conductometry 7 7 Gi) Coulometry —- Gv) Polarography w) ‘Amperometry J» Chromatographie Mcthods Introduction i). “Theory i) Classification of chromatograahic techniques Giii) Column Chromatography (iv) Paper Chromatography (w) Thin layer Chromatography wi) Gas Chromatography (vii) ULPIL.C, “Thermo analytical Methods . i @ Introduction. . @ Thermogravimetry Differential Thermal Analys's Differential Scanning Calorimetry ‘Thermometric Titrations Gi) )Introduction: Iise-common-observation-that whenever matter is heated through a wide temperature ranges it undergoes certain physical or chemical changes. These changes take place at | cerlain temperatures depending upon the material involved. For instance melting of a solid substance and boiling of a liquid shall occur at specific temperatures. A few other heat associdtcd changes may*be removal of water, change in crystal structure and polymerization etc, Like physical changes, chemical rcactions in solid state such as - decomposition of a carbonate or oxidation of a metal also occur at characteristic temperature range. Similarly most of the chemical reaction in solution form also involve the generation or absorption of a certain quantity of heat. Study of these changes along with the measurements of temperature or heat involved is the-basis of Thermal Methods of Analysis. By meastiing the temperature at which such physical or chemiéal changes occur and the heat involved in the change, one can characterize the substance ‘under study. A number of inorganic compounds, synthetic polymers and natural products have been characterized by thermal methods. The data obtained by heating a substance through a wide temperature range that ‘what type of change occurs at what temperature, not only cnables us to identify the material but also provides valuable information about :the thermal stability of the sample. . The major analytical techniques, based on heat-related properties are ‘Thermo gravimetric Analysis (TGA)Differential Thermal Analysis (DTA), Differential Scanning Calorimetry (DSC) and Thermometric Titrations (TT). . THERMBGRAVIMETRIC ANALYSIS Wow Thermogravimetry involves the measurement of change in weight of a’substance when it 7 is heated through a temperature range preferably. at a linear tate. Acnmentionedmearkeer ayat different changes take place at certain temperature when a sample is continuously heated; variation in weight is one of the common changes which occur at elevated temperatures. Most of the inorganic as well as organic substances experience a loss in thir weight on heating. The weight loss may be due to cither some chemical decomposition along with the evolution of a gas or removal of some molecules of water present as water of hydration or crystallization in the sample. ‘itil Decrease in the weight of precipitate on drying during a gravimetric analytical exercise: is a common experience, In fact thermogravimetry was’ born out of problems associated with gravimetric analysis. For a long time no particular temperature were assiyned for drying the various precipitates with the result that different research workers revealed different stoichiometric compositions even for the same precipitated compound ‘This was because of the amount of water driven off varied from one sct of conditions to another, [C who obtained thermogravimetric curves for a number of precipitate ludee their correct drying temperatures, solved the problem. - Trene ars Gwa bypes “hy TRermngnevimebtic — analatic Baya TEAede it Ups the Bergh vy Subfedat Lo oasis Soe urwalty Cinna vill Hraey oy aly Deemer ae iM Se ahd! « \ teed / p- fer a Pecied of (cma clusirg obichy any c in werghh are ndled, ~ 1Prine! igs Thermo gravimenr iis empentie te nee Roalysis is based on the change in the weight of @ substance as ee er Ree ete oem enter heated through a recorded. Although mena mperatre and simultaneously its weight and (empersiture are rraarded. Although manual recording of both the parameters is possible but usually an ae neg rau system iz used, The asembly tised for mzasuring and recording. the eight and temperature of a sample simultaneously over 2 predetrmy ed temperature gravimeter or a Thermo balance or a thermo gravimetric balance “TRERMOGRAM: ee of weight of the sample against the sample tempereture produced by a thermo s called d Thermo gram. For example the thermo gram of freshly prepared hydrated calcium oxalate is shown in fig Thé slopes and vertical paris of the curve reveal the ‘evolution of water, carbon monoxide and carbon dioxide from the sample whereas, horizontal parts indicate the species which are weight wise stable in that temperature range. Hydrated calcium oxalate has the following three distinct regions of decomposition: -> CaC,04 + 2H20 100-220°C 420-500°C “4 ° g 6 2° 1 > CaO +€0; 660-850% Spain ‘The thermo gram clearly shows that calcium oxalate forms stable compounds in the temperature ranges 240-400°C, 500-650°C and 860-1000°C. A few other thermo grams are shown'in figs Bntere) —- EQUIPMENT: : ‘A thermogravimetrie balance basically consists ofthe following three components: 1A furnace; to heat the sample at a linear rate through a given range of temperature. 2 A balance; to measure the weight changes in thé sample during heysing, 3 A recorder; to record temperature and weight constantly and plot ‘thermo gram. furnace Coble 4 FT daition to these dasic systems several auxiliary functions, which make the precise and accurate, have been incorporaled in commercially For example to avoid the atmospheric interferences during heating, provision of an inert atmosphere systems is generally available in most of the modern instruments. [pes & Decords| her mrobalancest. ‘There are humerous types of {GA instruments commercially available in the market. Basically all of them measure weight against the temperature increase. In etheds far continuous weighing of the sample, both single as well as double pan os ee used, These further inelude beam. spring. and torsion halanees. Some measurements more available instruments. ; Oy v3 Themen : ° T) Some ‘ Cyde Himes 4 ere Conrinen ( homie FE] malevial i Baan & netoal | : Peek i. n auto hee ~ c meat Si eadIco ey : je. Nul lity, reson he nee of dato wile ars wos in ll mods MUL weighing mechanisms are preferred in thermogravimetry as i es in weight, The in the same temperature region of the furnace irrespective of the changes img as semitivity.of a thermo balance and the maximum sample weight, which it can pecs without damage, is always co-related, Usually the maximum load of 1 ot Gag seusitivity of one microgram. Different types of sensors have been used 10 | tect the teviations of the balance bean from the null position. Typically anieleétio-optical device with a shutter attached to the balance beam is employed. The shutter partly blocks the tei path Between & kimp and a photocell. Movement of the beam resulting from the change in sample weight alters the light intensity. The change in light intensity falling on ihe photocell is used as @ measure of the mass change. Now-a-days in addition to the qanventional thetmogravimettic instruments micro-thermo balances are used for studying the kinetics of reactions in solid slate under isothermal conditions. FEATURES OF A GOOD THERMOBALANCE: A good thermo balance employ. ; ‘ed for serious analytical studies should must posses the following characteristics: : : i 1; A thermo balance should be of adequate accuracy, reproducibility and sensitivity. Kshould.be opera table through a wide range of temperature. 3: Furnace of the balance could be heated at a linear and adjustable heating rate. 4There must be some furnace cooling arrangement so that it should be ready for next sample in minimum possible time. 5: After heating the sample the container should not show any residual effects. 6 The balance should respond rapidly to changes in sample weight. 7: li should have high degree of electronic and mechanical stability, 8: The balance should not be affected by minor sowces of disturbances such as air currents, : ' 9: Furnace. sample container and thermocouple of the balance should be of some durable material. 10: The balance should be casy and simple in operation. I: There should be a provision of heating the sample under reduced pressure and inert atmosphere. a7 : i2: The balance should have a capacity to hold large samples: gs [istmo brllances t- ‘et CHEVENARD BALANCE “ ‘The first thermogravimetrc balance (shown in Fig.) was designed by Chevenard in 1944, ee ane iu gf oreanic compounds EIS by Dut and coworkers, around 1953. In his insient the sample was taken ina erucible, which an laced in the center of a furnace and connected with a counterweight to restore the Se a reer ore era A all aioe es ea balance needle, eee eree yt ae ae eee balance couldsin hrated hefore ae by using standard weights at the crucible end, A thermocouple employed to monitor the temperature of the furnace. In practice, the furnace was heated at a controlled rate starting from the lowest 10 ithest temperature (usually from room temperature 10 1000°C:). The variation in sample eight unbalanced the central beam and changed the mirror position. Consequently the Aeflection occurred in the path of light beam could easily be recorded on a photoserisitive calibrated r i “ 7 wh ba rated paper wrapped around the recorder. ] > + batts Cheve war As the Chevenard balance was the first ofertas design the instrument of its type it possessed a number of limitations. for example’it was a very delicate instrument which coiild be disturbed by shiking the table on which it was lyingtt did not have any cooling amangement so the fuinace required at least two hours cool.ng time after each sample before the next sample could be arialyzed“The balance did not have any provision for heating the sample under inert atmospher#Recording system was though sensitive but was not adequately reliable. AMINCO BALANCE Aminco balance is one of the modem commercial thermo gravimetric instruments used in analytical laboratories. This balance monitors the change in weight by the current generated in transducer cyil. In this system (as shown in Fig.) a sample holder is mounted ide @ glass or quartz Lousing, which is placed inside a furnace. The sample holder is connecied with a fine helical: spring through a transducer armature. A transducer coil fitted just outside and adjacent to the armature forms ‘a linear variable differential transformer. Any decrease in sample's weight causes the spring to contract and armature moves through the coil. ‘This movement generates an clectrical signal proportional to the weight loss of the sample. The electrical signal is transferred to an X-Y chart recorder, which i also connected to the temperature programmer of the furnace. The increase in the furnace temperature is continuously recorded along X-axis whereas the weight change is indicated along Y-axis JMduartegss _ Heating rate of furnace varies fron¥ 50C to 100°C per minute. ‘The “typical lemperaTCFETEMEEOT Aminco ‘Ihermo gravimeters are from ambient to 120°C’. Samples in the range 1 to 300mg can easily be analyzed with sensitivities downto —+fow, microgremrof-weight ehange. By evacuating or filling the glass housing with inert gas at certain pressure the sample can be heated under desired inert conditions. The Aminco balance is more reliable and easier to use than Che¢anard balance. FACTORS AFFECTING THE PERFORMANCE OF 4. TGA BALAN! In thermogravimetrie analysis. there are certain factors. which ean affest the efficiency of a TGA balance and'considerably influence the final results. In oner w wer petter performance fom a thermo gravimeter one should rnust keep these fyclars in vices ~ fees ow) nj gs These factors may be 4 divided into two. classes, wipe dl apeng cde a a rat Mior : py wa Oxted eee Havel Counter raedght Palonce poi ol -wo ~ i): Factors concerned with instrument. ii): Factors concerned with sample, with sample holder, furnace and ion of sample holder, furnace atmosphere, sitivity of ‘The Insumental factors are mainly concerned eonder of the balance. These include shape of the furnace, locat inside the furnace, heating rate, geometry of sample holder, . sensitivity and placement of thermocouple, stability of power supply unit, sen: reorder and calibration of balance. The major factors concemed with the sample are vature of the sample, quantity ofthe sample, physical state and particle size of the sample, solubility of evolved gases, heat of decomposition, sample packing and thermal conductivity of the sample, 2 . APPLICATIONS OF TGA: The pieces of information obtained by heating a substance and studying the changes through which it undergoes are not only valuable in chemistry but also in metallurgy, tngincering, ceramics and mineralogy. Other than these major fields TGA is also helpful in determining heat constants of various substances. Some of the important applications of TGA are as follow r 1. Drying/Ignition of Precipitates: The knowledge of correct drying or ignition temperatures for precipitates is of vital importance in gravimetric analysis, From a thermo gram one can easily decide that precipitate should be ignited completely or can be dried safely at a certain temperature. For example a continuous slope’ found in the case of ferric (Iil) hydroxide indicates the uncertainty in the composition of the compound due to gradual removal of water molecules. hence in the gravimetric determination of iron the hydroxide is ignited at above 300°C to iron (Ill) oxide. Contrarily a thermo gram of Ni(DMG), showed 'a horizontal line from 120°C to 170°C therefore this compound can be dried in this range to a constant weight. The study also facilitates the automation in gravimetric analysis. Hori portions of a thermogram provide the information about stability ranges from which new weighing compositions can also be deduced. 2. Qualitative/Quantitative Analysis: As-t-prisiciple every compound has its characteristic thermo gram. Whenever it j heated under a given set of conditions the same thermo gram should be obtained. This helps in identifying the compound even it is present in a mixture, Chraracteristie-themmo yams of afeweompoundsare shonin Figr x weight loss occurred in a chemical compound is always present in the sample. hence a quantitative analysis is al decomposition of magnesium oxalate always occurs accordin Proportional to its quantity Iso possible. For instance ig to the following equation: Mg(CO0):2H;0 - MgO + CO + CO) +2130Information about the wei: sul m" { loss experienced by a given weight of the sample is usually icient to calculate the percentage of magnesium oxalate in a given ore sample. ‘Thermal Decompositi,.n and ‘Thermal Stability: drape atty of thermal decomposition of various inorganic and organic substances is ways remained a subject. of curiosity for chemists. Earlier workers usually used.the total = in the weight of a compound to determine the stoichiometry of the residue, Now-a- Aue by TGA not only the study of step wise degradation of @ compound is possible but © composition of various intermediates which are stable at certain temperature ranges fn also be found. Moreover thermal decomposition in the absence of air or in an inert Amosphere, can easily be studied. TGA studies also reveal the thermal stability of a umber of industrial products such as paints, vamishes, packing materials, polymers, building materials, alloys and ceramics articles. This knowledge is important to the industrial chemists and concerned engineers because it reveals the temperature rangye over which these materials can safely be employed. Such information also helps to some extent in predicting the service lifetime of such substances. 4. Hygroscopic Studies and Kinetics of Reactions: , At ambient temperature certain compounds absorb water from air. By using, TGA hygroscopic character of such compounds can he studied at elevated temperatures and under control atmospheric conditions. Similarl{absorption of carbon dioxide from air by certain compounds cait he studied by thennogaavimeing Water molecules may be present along a cdmpound in more than one form such as waler_of hydration, water. of crystallization and water of co-ordination. By TGA one can easily differcntiate bolwech these different types of water moleculesSometimes purity of chemical compounds, especially of analytical reagents, becomes suspicious due to the presence of variable number of water molecules along with them. Purity of such reagents fan be asserted by thermogravimetrytiVKinetic studies. of chemical reactions are (another important application of thermbgravimenry.. Kinetics of well-defined thermal reactions can be determined by: plotting a series of isothermal curves of weight loss against time at different temperatures. These studies are often useful in ceramic and polymer industries. 5. Oxidation of Metals, Explosives, and Drugs: Corrosion or degradation of metallic objects in moist atmosphere usually occurs due to oxide formation on'thé surface exposed to air. By the help of thermogravimetry this phenomenon can be carefully studied at clevated temperature and under control aimospheric conditions. Contrary to most of the thermal phenomena like decomposition and dehydration exc. in oxide formation the weight of the given metal sample is increased due to the addition of atmospheric oxygen. Thermal studies of explosives and propellants A. provide information about their Mash points and oxidation mechanisms which help in ) problems such as hazards of their storage. ‘Thermogravimetry ‘also has applications in eata) ; pharmaceutical industry. The knowledge of the thermal stability range of various drugs Ielps in predicting theirshell life and storing conditions. Miscellaneous: » Applications In'addition to the above-méntioned important applications, thermogravimetry can te helpful in a large nurhnbet of academic and industrial fields.. Some of them are mentioned helow: (1): To study the sublimation behavior of various substances. (2): To separate the. volatile components of a-mixture and synthesis thew intermediate compounds. (3):-To find out physical constants such as vapor pressure, activation energy and binding energy. (4): To study the reactions at very high temperatures. (5): To confirm the stoichiometry of compounds by analyzing the evolved gases by gas chromatography during thermal analysis. (6): To evaluate different types of filter papers used for gravimetric analysi (7): The thermo gravimetric balance may be used for measuring magnetic susceptibility of compounds at high temperatures. DIFFERENTIAL THERMAL ANALYSIS ribhoctucbion One of the major drawbacks of thermo gravimetric analysis is that it can record only those changes, on heating a sample, which are associated with weight. Whercas there are a number of heat concerned, physica and chemical changes in which weight of the sample remains unchanged, therefore such changes cannot be detected by TGA. A few examples of such physical and chemical changes which: may not involve any variation in weight of the sample are melting, boiling, crystallization, oxidation, reduction and dissociation. These changes may be exothermic or endothermic. By Differential Thermal Analysis, DTA, such changes cannot only-be identified but the information obtained can be utilized in a number of applications. PRINCIPLE: In DTA, heat effects. associated with physical and chemical changes. are recorded as a function of temperature when the substance is heated at a linear rate. In other words” DTA is concerned with the rate of change of temperature’of a substance as it is heated at a constant rate.) Wheh @ Substance is heated slowly its temperature increases at» stern rate, Asa result ofthis heating when a physical or chemical change starts wo cake wee the temiperature stops to increase and remains constant until the change is = ¢ place After the completion of the change. as thé sample is being ented completed. temperature again starts (@ tise, The interval in temperature rise fet sisnerer ae ngeGccurred in the sample. The principle of DTA can be il‘ustrated by the following example. , “Suppose a sample of ice is started to be heated from -100°C at a steady rate. "Temperature of this piece of ice starts rising till il reaches to O"C. At this stage ice starts tomelt and temperature becomes constant at O"C. It will remain constant until whole the sample completely melts to water. After that the temperature will ayain start to rise. The same phenomenon shall be observed at 100°C where all the water has to be converted info steam: Temperature will remain constant at 100°C during this conversion. The isotherm in this case shall be a graph between the heat input and temperature rise.(The isotherm obtained in above example is shown in Fig. The horizontal sections of the curve represent the changes occurred by heating the sample) In practice an inert reference material is heated along with the sample under identical conditions and the temperature ofthe both are monitored constantly. At a certain temperature a physical or chemical change starts to occur in the sample, which causes a difference in the two temperatures, The difference, reflecting the change in the sample, is constantly measured and plotted as DTA isotherm. EQUIPMENT AND OPERATION: ‘The equipment used in DTA studies consists of the following essential componernts: Furnace or heat sink or some other device for providing heat at a constant rate. ‘ontainers to hold the sample and the reference material. iii): Thermocouples to monitor the temperature. iv):X-Y recorder to record the signals. dy Sapte AXldes = The instru rated by loading the sample and reference material’ in -respective crucibles, which are then placed into the heating block of the furnace. The dimensions and material of construction of the two cructbles should be as identical as possible. The crucibles for sample and referencé inaterial are usually made of some inert material such as alumina, borosilicate glass, fused quartz, zirconia, beryllia or graphite. Sometimes metals such as nickel, silver and platinum are also used for this purpose. ‘The weight of the sample and the reference material shouldbe virtually equal. Cit) Internal heaters'slowly raise the temperature of the heating block. The sample and the reference material are simultaneously heated and the temperature of the both starts to rise. The most commonly used temperature-measuring device is the thermocouple. which is.made froin some inert metals like platinum and rhodium. The junction of 4 thermocouple is placed in each of the crucibles in such a way that the voliage from each thermocouple generates an opposing electric signal on the X-Y reconler This males eee ropiegagreseed wees in temperatures between the sample and the reference, GHD X-¥ Chong’ as there'is no difference in the temperatures of sample and reference the electric signals produced by thermocouples cancel each other and there is no’ net stant At equal temperatures the recorder pen moves un-deflected even thers ‘actual temperatures of the sample and reffrence are increasing, When a change starts to tdke place in the samy gh the actual ple. the temperature of the sum| : becomes constant. Suppose that the change is aféndathermic. The sample will ie orb fhe : / oe “Ge.heat but that heat will be utilized in bridging the change rather than increasing the temperature, On the other hand temperature of the refercnee is constantly increasing. So a difference oceurs in the temperatures of the sample and the reference, which generates a net signal on the recorder. As soon as the change is finished, the temperature of the sample starts rising again and after some time becomes equal to the temperature of the reference. Simultaneously the recorder pen returns back to its original position. In the case of at’exothermie change sample becomes hotter than the reference and a net signal in opposite direction is produced. Hence the signals appear on a DTA thermo gram may be positive (upward) as well as negative (downward). A typical DTA thermo gram is shown in Fig, in which A, B, and C peaks show cndothermic changes and the peak ‘D indicates an exothermic change in the-sample, REFERENCE MATERIAL: i . i ion, in DTA, the sample is heated over a wide range of temperature along with ‘a reference material. The reference material should have the following characteristics: : : i):It should be thermally stable over the operating lemperalure range. it):It should be chetnically inert towards the sample holder, thermocouple, the gas in the furnace(if any) andithe sample. : iii):Most of the physical features such as particle size, quantity, heat capacity and thermal _tonductivity should be similar to those of the sample. Wypes off soferonce, i : Aluntina, AlzO3, and carborundum, SiC, have been extensively used as reference substances for inorganic samples. while for organic compounds, especially polymers, octyl phthalate and silicone oil are employed. Both solid samples and reference materials are usually used in powdered forin, The difference in particle size and the packing conditions may influence the results. Sometimes to improve the matching betwee physical features of the sample and “reference material, the samplé—is—"ailuted" (thoroughly mixed in solid state) with a certain quantity of the reference-material. Th Ss \eEfimique Improves the matching of thermal properties of the sample to those of the reference. There must obviously be no reaction of the sample with the reference material over the entire operating tentperature range: FACTORS AFFECTING THE RESULTS OF DTA ANALYSIS: ‘The factors. which can influence the results in the case of diffe analysis. may also be clastified into two major categories. First the factors conéemad with the various parts of the instrument and second those depending upon the characteristics of the sample. A third category of the factors may be due to the material used as reference Thé) instrumental factors are generally concerned with furnace, sample holder, temperature measuring device and the recording apparatus. For example, furnace atmosphere. size und shape of furnace and heating rate are the purameters concerned with furnace. Sample holder ‘geometry. material of construction, heat conductivity ot rential thermalveactivity, v% i ret eae tes of samples are the factors dhe 10 the’ container in whieh thermocouple in the sample ing. Similarly the range, sensitivity and location of important ins ple chamber and sensitivity and of recorder gre also portant instrumental factors to be considered. ony n ne thajor_ eet concerned with the sample include particle size, packing pees ae Sf sample. Some properties of the sample such as heat capacity, _ Rema conductivity, degree of erysallinity and change in'volume during heating ate aks worth considering prior fo analysis. Moisture content and chemical reactivity a aie nce material and sample holder can also affect the results. The factors necmes with the sample should equally be considered important for the reference material. each of the instrumental and sample factor play att important role in obtaining an informative and reproducible DTA curve. Change in any of these variables may affect the shape, size and position of the peaks and the overall reproducibility of the curve. DIFFERENTIAL SCANNING CALORIMETRY THEORY: se-far-TGA and DSC. are mostly Both th — Information like identification of used for qualitative and semi-quantitative analysis various substances, phase transformations, thermal stabilities and study of exothermic ind endothermic reactions can be readily obtained by these techniques. But in both the cases, as the changes are measured as a function of temperature, which is not a sensitive parameter to be accucately measured, hence in analytical terms only semi quantitative fata can be obtainee. Better quantitative data can be obtained by using differential scanning calorimetry DSC). PRINCIPLE AND OPERATION: * Differential Scanning Calorimetry (DSC) is not much different technique than DTA. In DSC also the sample is heated slong with 4 reference material through a programmed temperature range, However in the ease of a change in the sample. the temperature difference between the sample and the reference can be compensated by providing, extra thermal energy either to the sample or to reference. This additional gnergy. usually in form of electric current, which is provided to keep the sample and the reference at equal temperatures, 1s measured accurately, This electrical encreyScrve ran exact measure oF the change oct arthesample. [7S - apparatus used for DSC, is shown scvematically in Fig.ldentical quantities of sample and reference are -placed in respective cells in the heating block. Each cell is provided a separate additional heating coil, which remain inoperative as long as the temperatures of both the cells are equal. When a change starts:to occur in the sample, its temperature becomes slightly different than that oX-the reference. Difference in tric current ir the thermocouple system which is used to difference. This current activates an additional power-supply-to.the a lower temperature.In this way the temperature of the sample lly kept equal. The quantity of electrical energy used in Rifttence pan dS Recercher Syslem ‘to Bee Ceerd eleelycad cig | temperature generates an clecl detect the temperature heating coil of the cell at cand the reference are virtualhrating the eell. at lower temperature; and bringing its teriperature equal to the other jg rweasured accurately and recorded in form of a sharp peak on a recorder. sixnilar « eae mwas obtained in Differential Seanning Calorimetry are Siznitar to tose obtained in DTA but more accurate and reproducible. Like DTA, peal 2 Tine: the ardothermie and exothermic changes are recorded-on opposite sides of the base ference aca of peaks, which is a measure of the heat involved in sample or the re aie wimmately revesls:the nature and magnitude of the change occurred in the sample. Measurement of electrical cnergy in DSC enables the technique to provide a more curate quantitative data as compared to TGA arid DTA. APPLICATIONS OF DTA AND DSC: By the help of DTA and DSC'we can detect ail those weight concerned changes en sample, Which can be detected by TGA. In addition, however, DTA and DSC. can also study those physical and chemical changes, which do not involve weight variations. Such changes include structural changes, crystallization, phase changes and reactions in wolid state. Due th their large variety of applications, DTA and DSC are employed in fess and ceramics, mineralogy, metallurgy, engineering, polymer science, agriculture. industry, medicine and food analysis: A few important classes of applications of these lechniques are as follows: : ‘Identification of Substances: Thermograms obtained in DTA and DSC may be used as "“finger- prints" of various natural and synthetic substances, Comparison of these curves with sets of reference curves helps in identifying the substances. In a thermogram position of ‘lifferent peaks with refercnce to temperature is always a characteristic feature of a ‘particular compount. A characteristi¢ DSC curve of CuSO4.5H2¢ is shown in Fi DTA and DSC are extensively employed for i industrial materials such as clays and minerals, diffe and_greases, polymers, fats, p cOmpounds, rent types of fuels. Jubri proteins, amino acids, inorganic. oxides and_co-ordination, ii) Determination of Therthodynamical Constants: ‘Thermal techniques, in general. provide an information about the thermal stability of a substance. DTA is employed for determining some important thermodynamical Constants of umerous compounds of chemical and industrial interest. For esample 4 DTA curve can, provide a valuable information about heat capacity. heat of reaction, enthalpy, stability constant and thermal conductivity of a compound Differential Scanning calorimetry. as being a more accurate technique for quantitative preimmse ofien used for determining thermal constants of newly synthesised organic and inorganic compounds. ’iil) Studying Different Phenomena: DTA and DSC curves also help ‘in studying cerain physical and chemical Phenomena. For example reaction kinetics at clevated temperatures, — phase "ansformations, thermal degradation, solid state reactions and structural chemnges. in different compounds can be investigated by these thermal techniques, Similarly oxidation and reduction of compounds under special conditions of temperature, pressure and environment can be studied. DTA and DSC can identify co- existence of isomeric and allotropic forms in many compounds and elements. The techniques can also be used for Studying polymerization, dehydration, crystallization and sublimation behavior of a number of compounds. iv) Synthesis of Organic Derivatives: Thennal techniques, especially DTA and DSC, are not only used for studying chemical reactions and identifying new intermediates but also employed for the synthesis of derivatives of organic compounds. For this purpose the compound and the reagent are heated in a'DTA sample chamber at a programmed heating rate. ‘The resulting DTA curve reveals all the important steps of the derivative forming reaction. The technique has been successfully used for the formation of a number of organic derivatives such as acetone hydrazones derivative with p-nitro phenyl hydrazones and picric acid derivative with triethylamine. v) Crystallinity of a Polymer: m Polymers are usually made up of high molecular-weight compounds in which thousands of monomers are linked together in form of long chains, A polymer is usuiilly composed of fine crystals if the chains of equal sizes are: regularly oriented whereas an amorphous polymefic material is obtained when chains of different sizes are rumpled up haphazardly. Crystalline polymer is generally preferred as a raw material over the amorphous powder. Percentage of crystals in a given sample of polymer can be known by obtaining its DTA curve. The curves of two samples of the same polymer but with différent crystallinity are shown in Fig. A sharp peak in Fig (a), is resulted from the melting of polymer crystals The area of this peak is difectly proportional to the percentage of crystalline material in the sample. On the other hand a broad depression, shown in Fig (b), is. found when amorphous powder of the same polymer is heated under the same conditions. Che SN Heot [Tm Orerte: qa vi) Detection of Transitions at Low Temperatures: = Tora ; ye Fie > Up to a few years back, the changes occurring at elevated temperatures could Gul" be dotected by thermal techniques, Now-a- days DTA and DSC can also be used for studying the transitions which occur at low temperatures. In the market low temperature attachments are available for extending the, operating range of-temperature as low as ~ =p+ ey ' \ 175°C. By attaching a low temperature device with DTA or DSC instrumentation the transitions in the samples. which are liquid at room temperature, can also be studied. A thermo gram of CCM, obtained by performing DSC at Jow temperature range 1s shown in he thermo pra i i jon, about the structural I gram provides valuable information, abo. transformations of solid CCl4 at tow temperatures. Gqlaye Gransitiontenp. Study of Phase Diagrams: | * cro When a binary system, involving di the bio ebmponents, is ystem, involving different phases of the two components, heated or cooled, it is not usually possible to obscrve and detect all the changes, which occur in the system . ‘The D'TA and DSC thermo grams of such systems, obtained under completely controlled conditions and heating rates, help in explaining the exact nature of transitions involved in the system. By using DTA and DSC instrumentation, for studying a multi-phase. system, the constants like transition temperature; eutectic _point and equilibrium constants can easily and more accurately be measured. In addition, effects on parameters such as melting point, solubility and vapor pressure of different components due to cach other's presence can be studied, iii) Study of Reactions under Specific Conditions: Modern instruments used for DTA and.DSC usually have a provision of heating the sample under specific conditions. For example; with this provision, the sample can casily be heated under reduced piéssure or in an inert atmosphere. By taking advantage of this facility various organi¢ and inorganic reactions can be studi¢d under special conditions, The reactants are heated in the sample chamber. under desired conditions and a thermo gram is recorded. The resultant curve provides information about the kinetics and thermodynamics of the reaction, Processes like sublimation, degradation and combustion can be studied in.the presence or absence of air. ix) Applications in Ceramics and Metallurgy DTA and DSC are exceptionally useful techniques in glass and ceramics industry and metallurgical operations. In ceramigs; the technique is helpful for the qualitative and quantitative analysis of various raw materials, identification of the phase transformations Guring heating operation and standardizing the quality of final products. In metallurgy the structural transitions and other changes, which occur during sintering, fusing, roasting and other heat treatments, can readily bé detected. Identification of different components of alloys, detection of structural changes in the production of metal shects and wires and study of mechanisin of fatigue and other failure can also be made possible by DTA and qs. sources of metal 4) Attachment with other techniques: More valuable information about a compound or a system can be obtained by YDSC instruments with some other techniques, For example thermal interfacing DTA saan ee ance can be investigated in better way if the gases evolved during degradation of a substh eatme est weet alii sample are analyzed by feeding into 2.gus-chromatograph or a mass spectrom oo imal measurement off magnetic_susce nibiing of @ compound at Teen peratures during differential thermal analysis provides more valuable information about its structural changes. : THERMOMETRIC TITRATIONS THEORY Cn are Priveigle pape also called enthalpy titrations involve the measurement of heat generated. during a emical reaction, The sample is taken in an insulated container jtrated with a suitable titrant, The rise in temperature due to evolution of heat is measured and plotted against the volume of the titrant. Most of the chemical reactions are accompanied with the liberation of heat. Samples (A) + Titrant (B) --—--> Products (C) + Heat. _ When one mole of substance A reacts with one mole of substance Bs certain quantity of heat is produced which is called heat of reaction. Heat of reaction is colligative property of the reactants in a particular reaction. If the titrant B is present in excess, the quantity of heat generated will depend upon the quantity of sample A. So the splationship-betweet the heat evolved_and-the-quantity-of-sample-is-sctually utilized i thermometric titrations. : Tn practice, a known volume of sample is taken jn an insulated flask, Suitable aliquots of the titrant are added either continuously or with equal intervals of time and temperature of the mixture is constantly recorded, AAs the titrant is added, io start the temperate increases regularly. After the end point, when all the sample hs been rvrned, the temperattwot the mixture steadily decrease as the mixture is dliluted by adding the cool titrant. Temperature readings are then plotted against the tirari volume to Sbiain a titrdtion curve. A sharp turn in the curve indicates the end point. A typical cs curve obtained by the reaction of sodium hydroxide and hydrochloric acid is shown in fig. (A) INSTRUMENTAL serur: , Fer" shewwos moles ‘A schematic diagfm of the instrumental Setup used for thermometric titration is shown in fA Known Volunve of sample is taken in a thermally insulated Dewar flask D- sa ig equipped with a mechanical ster S. Suitable aliquot’s of titrant from the which tive tansfersed into the reaction flask with the help of a thermo stated motor- sure of the mixture is monitored by highly sensitive thermistor, driven burette B, Teraperat dipped into the solution and attached to recorder through @ D.C. bridge circuit. Recorder is calibrated with the addition of titrant by the motor-driven burctte. The physical parameter of the instrument varies widely from apparatus to apparatus. The factors which can influence the roiling the, volume of titration Naot +HG—> 3-SRel Ani (heat ry noubie~ flask, rate of addition of titrant, thermistor sensitivity, concentration of the reacting solutions and sensitivity of the recorder, APPLICATIONS OF THERMOMETRIC TITRATIONS: Thermometric titrations ‘have been successfully employed: for neutralization, complexation, redox and precipitation reactions. As the dielectric constant of the solvent has no effect upon the results, these titrations are equally useful for non-aqueous systems. In addition these titrations can, also be used to titrate liquid solutions against gascous reagents. A large number of titrations have been carried out to determine enthalpy changes in various aqueous and non-aqueous systems. Acid-Base Titrations: As neutralization reactions mostly accompanied by the generation of a significant amount of heat, therefore a large mumber of acids and bases have been successfully analyzed by thermal titrations. These include HCI Vs NaOH, NH40H Vs HCI, H3P04 Vs NaOH and H3PO3 Vs NaOH. Organic acids such as monochloréaéetic acid, glutamic acid and trichloro acetic acid can be titrated with sodium hydroxide whereas bases like pyridine and aromatic amines can be titrated with hydrochloric acid. Precipitation Titrations: “Thermomettic titrations can also be employed for precipitation reactions. The heat of reaction in such system is also large cnough and hence a workable titration curve can be oblained. Following systems have been studied by this technique. Ag! Ys Cl" Ca Vs C204", Hg” Vs I" and Ni* Vs CN’ Complexometric Titration “Thermometric titrations have been successfully employed for the determinations of lead, Cadmium, Copper. Nickel. Calcium, Zine and Cobalt by titrating separately against EDTA. However accuracy in complex metric systems highly depends upon the sensitivily of temperature (change in temperature) recording. Oxidation-Reduction Titrations: ‘Though not much work has been done in the field of thermal redox titrations but still a number of titrations: involving cerium(1V) and permanganate ions as titrant have been carried out successfully. Ions like lron( lI), Titanium(II1) and Hydrogen peroxide can, be titrated against Cerjum(IV) while permanganate may be used for oxalic acid and ferrocyanide.