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Thermal Methods
Thermogravimetry (TG) Differential thermal analysis (DTA) Differential scanning calorimetry (DSC)
Karl Fischer (German chemist) developed a specific reaction for selectively and specifically determining water at low levels.
reaction uses a non-aqueous system containing excess of sulfur dioxide, with a primary alcohol as the solvent and a base as the buffering agent A modern KF titrator
[RNH]+SO4CH3 + 2[RNH]+I-
Two methods:
Conventional (Fritted cell): frit separates the anode from the cathode Fritless Cell: innovative cell design (through a combination of factors but not a frit), impossible for Iodine to reach cathode and get reduced
pH
Optimum pH is 4-7 Below pH 3, KF reaction proceeds slowly Above pH 8, non-stoichiometric side reactions are significant
Other errors:
Atmospheric moisture is generally the largest cause of error in routine analysis
When operated properly, KFT can yield reproducible water titration values with 2-5% w/w precision
E.g. sodium tartrate hydrate (15.66% water theory) usually yields KFT values in the 15.0-16.4% w/w range
Uses: Insoluble materials (plastics, inorganics) Compounds that are oxidized by iodine
Results in anomalously high iodine consumption leading to an erroneously high water contents Includes: bicarbonates, carbonates, hydroxides, peroxides, thiosulphates, sulphates, nitrites, metal oxides, boric acid, and iron(III) salts.
Thermal Analysis
Thermal analysis: determining a specific physical property of a substance as a function of temperature
In modern practice: The physical property and temperature are measured and recorded simultaneously The temperature is controlled in a pre-defined manner Classification: Methods which measure absolute properties (e.g. mass, as in TGA) Methods which measure the difference in some property between the sample and a reference (e.g. DTA) Methods which measure the rate at which a property is changing
TG Instrumentation
Components:
Sensitive analytical balance Furnace Purge gas system Computer
Applications of TGA
Composition Moisture Content Solvent Content Additives Polymer Content Filler Content Dehydration Decarboxylation Oxidation Decomposition Decomposition of calcium oxalate Sample Weight
H20 Ca(C00)2 CO CaC03
CO2 Ca0
200
400
600
800
1000
TGA
File: Y:...\TGA\SB332235\CL42969-112A1.001 Operator: J Brum Run Date: 18-Feb-05 14:45 Instrument: TGA Q500 V6.3 Build 189 1.2
1.0 80 0.8
60
0.6
0.4
0.2
0.0 350
Universal V3.8B TA Instruments
Temperature (C)
DTA Instrumentation
H (+) endothermic reaction - temp of sample lags behind temp of reference H (-) exothermic reaction - temp of sample exceeds that of reference
Endothermic Rxns: fusion, vaporization, sublimation, ab/desorption dehydration, reduction, decomposition Exothermic Rxns: Adsorption, Crystallization oxidation, polymerization and catalytic reactions
Applications of DTA
simple inorganic species
Phase transitions
determine melting, boiling, decomposition polymorphism
Jacobson (1969) - studied effects of stearic acid and sodium oxacillin monohydrate
DSC Instrumentation
There are two common DSC methods Power compensated DSC: temperature of sample and reference are kept equal while both temperatures are increased linearly Heat flux DSC: the difference in heat flow into the sample/reference is measured while the sample temperature is changed at a constant rate
Applications of DSC
DSC is usually carried out in linear increasingtemperature scan mode (but can do isothermal experiments)
In linear scan mode, DSC provides melting point data for crystalline organic compounds and Tg for polymers
DSC trace of polyethyleneterphthalate (PET)
Easily used for detection of bound crystalline water molecules or solvents, and measures the enthalpy of phase changes and decomposition
Applications of DSC
DSC is useful in studies o polymorphism in organic molecular crystalline compounds (e.g. pharmaceuticals, explosives, food products) Example data from two enantiotropic polymorphs
DSC
File: Y:...\DSC\SB332235\CL42969-112A1.002 Operator: J Brum Run Date: 24-Feb-05 09:53 Instrument: DSC Q1000 V9.0 Build 275
0.0
56.35C 34.97J/g
134.06C 116.0J/g
-0.5
84.39C
-1.0
Loss of water
153.30C
Melt
-1.5 0
Exo Up
Decomposition
150 200 250 300
Universal V3.8B TA Instruments
50
100
Temperature (C)