Thermodynamics Basic principles

UMF Carol Davila Dept. of Biophysics

Thermodynamics (basics) (AP)

What is thermodynamics?

The science of reciprocal transfer of energy within a system and between different systems

UMF Carol Davila Dept. of Biophysics

Thermodynamics (basics) (AP)

Questions, discussion:

Describe the energy flow and transformations necessary for a grain of wheat to become a slice a bread The greenhouse effect:

Wikimedia Commons UMF Carol Davila Dept. of Biophysics Thermodynamics (basics) (AP)

Thermodynamic systems

Thermodynamic system = macroscopic system,

composed of a large (but finite!) number of particles, which interact energetically among them and with the exterior environment

UMF Carol Davila Dept. of Biophysics

Thermodynamics (basics) (AP)

Which one is a thermodynamic system?

UMF Carol Davila Dept. of Biophysics

Thermodynamics (basics) (AP)

State of a system state parameters

Measurable physical amounts, that define the state

Temperature Pressure

Intensive parameters:

Not influenced by the size of the system

Number of mols Mass Volume

Extensive parameters:

Depend on the size of the system

UMF Carol Davila Dept. of Biophysics

Thermodynamics (basics) (AP)

State parameters

Temperature a measure of the thermal motion

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Wikimedia Commons

Pressure reflects the force of the molecules hitting the container's walls, divided by the surface of the walls

UMF Carol Davila Dept. of Biophysics

Thermodynamics (basics) (AP)

Connection between p, V and T

Ideal gas law:

pV = RT

p pressure V volume - number of mols R universal gas constant

(R = 8.314 J/kmol K)

T - temperature

UMF Carol Davila Dept. of Biophysics

Thermodynamics (basics) (AP)

Questions, discussion

Explain, for an isolated thermodynamic system, considering the molecular explanations for temperature and pressure:

What happens to the pressure of a gas, maintained at constant volume, when temperature increases What happens to the volume of a gas, maintained at constant pressure, if the temperature increases What happens to the pressure of a gas, maintained at constant temperature, if the volume increases

UMF Carol Davila Dept. of Biophysics

Thermodynamics (basics) (AP)

UMF Carol Davila Dept. of Biophysics

Thermodynamics (basics) (AP)

Thermodynamic process

Evolution of a thermodynamic system from one state to another Reversible processes:

Cvasistatic (at any moment in time, the system is at equilibrium) If the sense of variation for the thermodynamic parameters is reversed, the system returns to the initial state following the same pathway (it goes through the same states, only in reversed order)

Irreversible processes

Non-cvasistatic If possible, the return to the initial state is on a different pathway and requires external interference

UMF Carol Davila Dept. of Biophysics

Thermodynamics (basics) (AP)

UMF Carol Davila Dept. of Biophysics

Thermodynamics (basics) (AP)

http://members.fortunecity.com/rickteuscher/index.html
Thermodynamics (basics) (AP)

UMF Carol Davila Dept. of Biophysics

Questions, discussion

After a few hours of driving, the temperature inside the tires of a cars increases from 17C to 27C. What's the relative increase in pressure? When will the volume of a gas inside an isolated elastic balloon (p = ct) increase more (no gas escapes the container) ?:

When 10 l of hydrogen are heated with 10C When 10 l of carbon dioxide are heated with 10C

UMF Carol Davila Dept. of Biophysics

Thermodynamics (basics) (AP)

Thermodynamic equilibrium

State parameters are constant spatially, within the system, and don't change over time The spontaneous evolution of a thermodynamic system is towards equilibrium

UMF Carol Davila Dept. of Biophysics

Thermodynamics (basics) (AP)

The principles of thermodynamics

Principle 0

Transitivity of thermal equilibrium (if object A is in thermal equilibrium with object B, and B is in thermal equilibrium with C, then A and C are in thermal equilibrium)

Principle I

Conservation of internal energy

Principle II

Entropy; spontaneous direction of evolution for thermodynamic systems

(Principle III)

The entropy of a system approaches 0 when the temperature approaches 0 K.

UMF Carol Davila Dept. of Biophysics

Thermodynamics (basics) (AP)

The Ith principle of thermodynamics

Internal energy of a system extensive state parameter

total energy of a system

Kinetic energy: Translational Rotational Vibrational

Potential energy Attraction between molecules Interaction with external fields (electric etc) Intramolecular, intraatomic energies

time

The variation of internal energy of a system depends on the initial state and the final state, but not on the pathway of evolution between states
Thermodynamics (basics) (AP)

UMF Carol Davila Dept. of Biophysics

Mathematical expression of the I principle of thermodynamics

U =Q L

th

The internal energy of a system (U) increases when the system receives heat from the exterior (Q) and decreases when the system does work (L) Heat energy transfer due to chaotic movement of molecules
(Q > 0 when the system receives heat)

Work energy transfer due to ordered movement of the system

(L > 0 when system does work)

UMF Carol Davila Dept. of Biophysics

Thermodynamics (basics) (AP)

Conservation of energy

Ith law of thermodynamics = ENERGY CONSERVATION LAW

The energy is never lost, it changes from one form to another Isolated system conservation of internal energy (U = 0)

Impossibility of construction of a perpetuum mobile:

No machine can be build to produce work without energy input

UMF Carol Davila Dept. of Biophysics

Thermodynamics (basics) (AP)

II law of thermodynamics - Entropy

nd

State parameter Expresses the disorder in a thermodynamic system

Q S= T

Q heat exchanged by the system with the exterior T temperature

UMF Carol Davila Dept. of Biophysics

Thermodynamics (basics) (AP)

II law of thermodynamics - Entropy

nd

Boltzmann definition

Entropy expresses the order among the particles from which the system is made

S = k ln N

k Boltzmann's constant (1.38 10-23 J/K) N thermodynamic probability of a state

Number of distinct microscopic states corresponding to a macroscopic state

UMF Carol Davila Dept. of Biophysics

Thermodynamics (basics) (AP)

II law of thermodynamics - Entropy

nd

UMF Carol Davila Dept. of Biophysics

Thermodynamics (basics) (AP)

Spontaneous evolution of thermodynamic systems

Increased entropy
All spontaneous processes occurring in an isolated thermodynamic system lead to:

Decreased free energy (part of the

internal energy of a system that can be transformed into work)

UMF Carol Davila Dept. of Biophysics Thermodynamics (basics) (AP)

Author: David van der Spoel, Uppsala University (Sweden), spoel@xray.bmc.uu.se Title: Picosecond Melting of Ice by an Infrared Laser Pulse: A Simulation Study

UMF Carol Davila Dept. of Biophysics

Thermodynamics (basics) (AP)

Questions, discussion

How is the entropy changing in the following examples of thermodynamic processes:

Protein synthesis Aging of a biological organism Digestion of nutrients Water heating

What happens to the entropy of an isolated system? What happens to the entropy in a reversible process?

UMF Carol Davila Dept. of Biophysics

Thermodynamics (basics) (AP)

Supplementary readings

http://web.mit.edu/16.unified/www/FALL/thermodynamics/ http://www.slideshare.net/ercolino/introductory-biological-thermodynamics http://llk.media.mit.edu/projects/emergence/index.html

UMF Carol Davila Dept. of Biophysics

Thermodynamics (basics) (AP)