Physical Biochemistry Lecture notes Principles of thermodynamics States of matter descriptions (pressure, temperature, amount) Basic concepts of heat

t and work and internal energy First Law conservation of energy; heat capacity; enthalpy; thermochemistry; variation with temperature Second Law entropy and spontaneous reactions Third law of thermodynamics

Thermodynamics is the science of energy transfer it is a generally applicable and can tell you whether a reaction is can take place or not however what it cannot tell you is the speed of the reaction. Heat is a form of energy caused by molecular motion. Temperature is how hot an object is Newton developed a scale between 1- 12. Fahrenheit used freezing of body temperature of a salt solution and body temperature with 96 division in between .this lead to the Fahrenheit scale where 32F is the temperature that ice melts,96F is body temperature and 212F being the boiling point of water. Celsius assigned freezing as 0c and boiling point as 100c Kelvin scale 0c = 273.15 k Energy in relation to system and surroundings - A system is collection of matter under study - Surroundings are the environment that is in contact with the system and may influence the behaviour of the system. - Temperature is an intensive state function as is does not depend on the size of the system - Mass is an extensive state function as it does depend on the size of the system Types of systems

Work Work is the transfer of energy from one state to another in an ordered system whereas heat is random molecular motions so the total energy a system has can be split between the heat and the work Both work and heat are forms of energy and are expressed as joules

Wok and heat interrelate E.g. Say we have piston and this piston has a mass on it and inside the piston is combustible liquid occupying a specific volume and pressure M= mass P1v1 =pressure and volume H1 = the height of the piston

Now if that liquid ignites it forces the piston up this changes the H1 to H2 and because of this change in h1 it has an effect on the v1 v2 the same amount of molecules are now occupying a larger area the pressure and volume changes as a result

Formula Work = force x distance

However in this instance we have work being performed by the system by the surrounding therefore then a minus is introduced in the formula. If we have work performed by the system by the surrounding then we have a positive sign Work = - force x distance Now force is defined as mass x acceleration So the real equation is Work = - (mass x acceleration) x distance So its m x g x (h2 h1) Work performed on the system by the surrounding is a positive + Work performed by the system on the surrounding is a positive -

Work is defined as the force acting against the process and so its the external pressures that need to be considered

(Pext)
PRESSURE = force /area = mg/A W= - Pext A (H2-H1) OR W= - Pext V

1st law of thermodynamic

The sum of all energy change in an isolated system is zero Energy cannot be destroyed or created it can only be transferred Forms of energy = electrical, gravitational, chemical, radiation, thermal, mechanical, nuclear
The forms of energy can change E.g. Electrical to mechanic is in motors Gravitational to mechanical as in a falling weight Thermal to radiation (light bulb) Nuclear to thermal as in nuclear fission

Enthalpy H is a key concept in bioscience as it gives information regarding the bonds present in a material If bonds are broken energy is absorbed from the surrounding H is + (ENDOTHERMIC) If bonds are made energy is lost to the surrounding H is (EXOTHERMIC) NB To break bonds you need energy H is + (ENDOTHERMIC To create bonds you loses energy H is (EXOTHERMIC) Enthalpy of formation HF can e calculated from the constituents of its atoms Enthalpy of combustion can be measured using a bomb calorimeter

The calorimeter is filled with at a very high pressure about 30 atm. The sample is ignited using electrical contacts Temperature change is measured via a thermometer By knowing the specific heat capacity of the sample how much energy it requires to raise a unit of the substance by a specific temperature ) enthalpy can be calculated

The standard enthalpy change of combustion HC is the enthalpy change when one moles of a substance burn completely in oxygen under standard conditions This is an exothermic reaction so the H is negative and the answer is always in kJ mol The standard enthalpy change of formation Hf is the enthalpy change when one mole of a substance is formed from its constituents Measuring the HC bomb calorimetry Used equation energy transferred = m x c x T

Hesses law Hesses law states that as long as the starting and end products are the same it does not matter which route you used to get there the chemical reaction will be the same from start to finish The cycle is used in finding the enthalpy changes of unknown from known

Entropy Entropy (S) is related to disorder and probability 2nd law states that the entropy of an isolate system will either increase or stay the same but it will never decrease Disorder tents to increase the probability of an reactions likely hood to occur.

Molecular motions - entropy is also associated with molecular motions (rotational, vibrational) that do not perform work Reactions that will result in a decrease in these motions do not tend to be favoured These motions are (almost) always present and increase with increased temperature They also decrease with decreased temperature Can we come to a point when they stop altogether?

1st/2nd laws of thermodynamics

First law lead to internal energy it allows us to assess whether a reaction/process is permissible. A non-permissible reaction process is one in which the internal energy of an isolated system does not remain constant e a system does work without consuming heat or work from the surroundings.

Second law tells us out of all the permissible reactions which ones will proceed spontaneously. i.e. unforced. t gives the direction of unforced change and therefore gives the criterion of spontaneity. NB: Thermodynamics tells us nothing about the rate at which a process Occurs Degree of disorderedness Is related to the transfer of energy as heat It is heat which stimulates a change in ordediness. Work stimulates uniform motion of atoms in the surroundings and so does n change the degree of disorder. In fact work has to be done to counter the effects of growing disorder. It requires effect to keep your room tidy. The impact of a small change in temperature on entropy is small at high temperatures where there is much disorder but much greater at low temperatures where there is high state of ordering. This suggests a 1/T relationship.

Gibbs free energy The probability of a reaction occurring spontaneously or it occurring due to outside influences this is decided by the balance entropy and enthalpy Free energy (G) is the arbiter between the two The Gibbs equation is G =H-TS G = change in free energy H-TS = The change in the enthalpy ( H) of the system minus the product of the temperature (Kelvin) and the change in the entropy ( S) of the system: Gibbs Free Energy (G) - The energy associated with a chemical reaction that can be used to do work. The free energy of a system is the sum of its enthalpy (H) plus the product of the temperature (Kelvin) and the entropy (S) of the system:

If the G is negative then the system can perform work on the surrounding and the reaction will be spontaneous If the G is positive then the system is not able to perform work on the surroundings and the reaction will not be spontaneous