Phreeqc教程2 -热力学数据库.pptVIP

Calorimetry Measurement of heat flow (through temperature) associated with a reaction Because dH = q / dT, measuring Temperature change at constant P yields enthalpy Hess’s Law Known values of DH for reactions can be used to determine DH’s for other reactions. DH is a state function, and hence depends only on the amount of matter undergoing a change and on the initial state of the reactants and final state of the products. If a reaction can be carried out in a single step or multiple steps, the DH of the reaction will be the same regardless of the details of the process (single vs multi- step). CH4(g) + O2(g) -- CO2(g) + 2H2O(l) DH = -890 kJ If the same reaction was carried out in two steps: CH4(g) + O2(g) -- CO2(g) + 2H2O(g) DH = -802 kJ 2H2O(g) -- 2H2O(l) DH = -88 kJ Determining Entropy As for H, dS=q/dT ? can be measured as heat energy (q) Another way to think of entropic energy – for any reaction, energy is ‘dispersed’ to/from the surroundings –measured from 0K (actually just close to it), where S0=0 for ANY substance (at 0 K, atoms do not MOVE!) S0 for water = 69.9 J/mol Entropy detemrination S0 for water = 69.9 J/mol 0 K to 298 K what happens to water? Heats up, changes phase (ice-ice ? liquid) 69.9 joules/mol is a very small part of that energy! How to evaluate that small heat change – CAREFULLY determine Cp over this range in incremental steps to subtract H component Theoretical estimations In natural systems, there are many species, minerals, gases that are very difficult to impossible to determine with any accuracy by experiment Correlation methods based on isostructural-isovalent analogues, electrosatic models, ligand field models exist, but are based on empirical evidence and have little grounding in theory – thus these often suffer from innaccuracy (if that is even known!) Theoretical determinations Ab initio (first principles) calculations based on electron energy (complicated rules for ESTIMATING this) can be used to determine enthalpy