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Department of Bioorganic and Biological Chemistry. Bioinorganic chemistry I COURSE LECTURE 2. THE CHEMICAL THERMODYNAMICS AND BIOENERGETICS LECTURER: Professor A.D.DZHURAEV PURPOSE OF LECTURES: • Give an idea of thermodynamics, noting the universality of the laws of thermodynamics to the animate and inanimate nature. • Acquaint with the basic laws of thermodynamics, to give an idea about the systems and their types. Provide insight into the relationship between the processes of metabolism and energy in the body. To familiarize with the laws of thermodynamics, drawing attention to the irreversible processes in the body. THE LECTURE PURPOSE: • The notion about laws of the thermodynamics are given, as they universal for alive and not alive nature. Must know, as it is filled up the lost by organism energy in process of vital activity, and what types of energy is act in organism. The breach of the energy exchange is a reason of the row of hard treatment diseases of the person therefore physician must know the mechanism of the transformation different material in energy. DEALT of questions • The object and purpose of thermodynamics • The value of the laws of thermodynamics in medicine • Thermodynamic systems and thermodynamic parameters • The internal energy • The first law of thermodynamics • Isobaric and isochoric heat effects • Enthalpy DEALT of questions • Chemical Thermodynamics. thermal effects • Hess's Law and its consequences • The second law of thermodynamics • Entropy and Free Energy • Conditions of thermodynamic equilibrium • Spontaneous thermodynamic processes and conditions of their orientation The subject of thermodynamics Thermodynamics -- the science of the laws of different types of energy transformation in each other. Its object of study - thermodynamic systems Systems and their classification... • Part of the space arbitrarily limited the interface from the environment is called a system. • On the principle of exchange with the environment of the system are: • Open - exchange of matter and energy and • Closed - only exchanged energy • Isolated - do not share neither substance nor energy Thermodynamic system and its internal energy • Any system characterized by the so-called state of thermodynamic parameters - mass, volume, pressure, temperature swarm, composition, specific heat, and internal energy. • The internal energy of the system - a combination of all kinds of energy in the system. • U = Ukinetic + Upotential + Uвн Uвн = U2 - U1 The first law of thermodynamics • In any process of energy does not disappear and does not appear out of nothing, it just changes from one form to another in equivalent amounts. • The first law of thermodynamics, applied to the activity of a living organism • The chemical energy of metabolism is transformed into other forms of energy and allows the flow of the vital processes in the body. The mathematical expression of the first law of thermodynamics U = Q – A or Q = U + A Where: Q – the amount of heat U – Changing the internal energy:: A - amount of work is done under the effect of external forces Chemical Thermodynamics • Section thermodynamics studies of energy conversion in chemical process called chemical thermodynamics • Processes occur with heat are called exothermic processes occur with the absorption of heat are called endothermic • The amount of heat absorbed or released in the course of chemical reactions called the heat of reaction. Hess's Law "The thermal effect of the chemical reaction (enthalpy) depends on the type and condition of the starting materials and reaction products and not on the path of transition from the initial to the final “ Q = Q1 + Q 2 = Q 3 + Q 4 + Q 5 Q1 Q2 Q Q3 Q5 Q4 Hess's Law Pb + S + 2O2 = PbSO4 + 919,7 I. Pb + S = PbS + 94,5 II. PbS + 2O2 = PbSO4 + 825,2 919,7 The thermal effect of the isothermal process An isothermal process t = const, heat is transferred from one body to another without changing the temperature, than, Q т = рV Thermal effect isochoric process Isochoric process when the volume is constant, than, V = const With unchanged quantities: V = 0 when work is not done: рV = 0 In such conditions, according to the first law of thermodynamics, the total amount of heat supplied to the system spent to increase the internal energy: QV = U Thermal effect of isobaric process When the process of isobaric pressure is constant: P = const For such a state of expression for the first law of thermodynamics Q = U + р V is rewritten as follows: QP = U2 -U1 + р(V2 -V1) = U2 - U1 + рV2 -рV1 QP = (U2 + рV2) - (U1 - рV1) The thermal effect at constant pressure is called the enthalpy of the system and is denoted by H: U + рV = H then: QP = H2 - H1 = H Heat spent to increase its enthalpy The second law of thermodynamics The heat is not transferred spontaneously from a cold to a hot body, ie If any form of energy can be converted into heat in the case of the reverse transformation of heat into any energy, complete conversion can not be. Entropy Entropy is the ratio of the heat of reaction to the absolute temperature, S = Q \ T Logarithmic value of the thermodynamic probability of a system is called entropy:S = k lgW Here: S - entropy - disorder in the function of the system; k - Boltzmann constant W - thermodynamic probability Entropy. Standard entropy The entropy determined at standard conditions (T = 2980K, p = 101.3 kPa) is called the absolute value or the standard entropy and designated S0 298 (∆S0 298) = ∑( S0 298)product - ∑( S0 298) outgoing materials Example calculation of standard entropy С( ) + СО2 (g) = 2СО(g) 5,7 213,7 197,5 Standard entropy will be: S0 298 = 2( S0 298) СО – [( S0 298)С + (S0 298)СО2] = = 2 - 197,5 - ( 5,7 + 213,7) =175,6 joules (mol K) Gibbs energy. 1. Free energy - the energy that can be converted into work 2. Bound energy - an energy that in the process can not be converted into job. G = H - T * S or ΔG = ΔH - TΔS, G - Gibbs energy ΔH - enthalpy factor TΔS - entropy factor Parameters calculated for the direction and feasibility of the thermodynamic process: • ΔG <0 - spontaneous process, a transition of the system from the initial state to the final • ΔG = 0 - the system in balance • ΔG> 0 - a transition from the initial to the final • thermodynamic process: