1. Thermodynamics and Chemical Equilibrium Flashcards
What characterises a solid? What forms may solids take?
Particles packed tightly together and are not able to vibrate around fixed positions.
May be crystalline (arranged in regular ordered patterns) or amorphous (not arranged in regular patterns)
What are some defects in the crystalline structure of solids (4)?
Vacancies: Atom/molecule is missing from its place in regular pattern
Interstitial defects: extra atom/molecule in position between the usual locations of the pattern
Line defects: plane or regular pattern stops abruptly in middle of crystal
Planar defects: complete misalignment between crystal structure on either side of a plane through solid
What are the amorphous and crystalline forms of silicon dioxide?
Amorphous: glass
Crystalline: quartz
What characterises a liquid?
Particles free to move relative to each other, may be locally ordered but no long range order. Liquids are incompressible.
What characterises a gas?
Fluid (like a liquid) but much less dense, particles are in constant random motion. Collision between particles may lead to formation of a dimer.
What is the equation for pressure?
Pressure = Force / Area
Pressure of a gas is related to the force exerted by the gas molecules every time they collide with the sides of the container
What is equal to the force exerted by a molecule during collision with a wall? What does this mean?
The rate of change of momentum of the molecule.
Therefore the greater the component of the molecules velocity in the direction of the wall (before the collision) the greater the force exerted by the molecule
Which factors affect gas pressure?
number of molecules, temperature and volume of the container (n, T, V)
As n increases, P increases
As T increases, P increases
As V increases, P decreases
Define temperature
The average speed of the atoms/molecules in the gas
What is the ideal gas equation?
pV = nRT (R=8.314 J/mol/K
What is the fourth state of matter?
Plasma, a gas in which a portion of the molecules have been ionised. Removed electrons remain part of the plasma so it is electrically neutral. Constituents of plasma interact strongly via electromagnetic fields - so plasma behaves very differently to a gas
Give examples of some of the other, less common states of matter
Glasses, liquid crystals, superfluids, quark-gluon plasma
What is the name of the process converting solid to gas?
Sublimation
What is the definition of a liquid solution?
A homogenous mixture of two or more distinct chemical species in the liquid phase
Can also have solid solutions
Is a pure liquid a solution?
No
Is milk a solution?
No, complete homogeneity is required for a solution and milk has two fluids which are immiscible and form an emulsion
What is relative permittivity (epsilon r)?
Dielectric constant -a measure of how well the solvent is able to store electrical energy by concentrating lines of electrical flux - it is a measure of polarity
What is viscosity?
A measure of the resistance to flow. Important when considering mobility of solute molecules (in the solvent).
What solvent trait may increase solubility?
ability to form hydrogen bonds
What is the name of an ionic solute?
an ELECTROLYTE ZAP ZAP
What do the properties of the solute molecule depend on?
The nature of the solvent and the amount of the solute
What is the shortening used for solute and solvent?
Solvent = A Solute = B
What is an ideal solution?
A solution where the solute molecules interact with the solvent molecules in the exact same way they interact with each other.
How would you ensure that the greatest dissolution occurred?
Make sure the solute and solvent behaved as similarly as possible (most similar interactions) - ‘like dissolves like’ - the closer to ideal solution the better
What are the different types of interaction that may occur between molecules?
Ionic (strong, long range), covalent (strong, short range), Van der waals (weak)
Describe the three Van Der Waals forces
Keesom forces: between molecules with permanent dipole moments (Asymmetric charge distributions)
Debye forces: between one molecule with permanent dipole moment & one with transient dipole moment
London forces: between two molecules, neither of which has a permanent dipole, interaction is as a result of mutual instantaneous induced dipoles
If dissolving a highly polar/ionic substance what type of solvent would be a good call?
A solvent with a high relative permittivity - e.g. water 78.54
What are the relative permittivity relative permittivity of water, ethanol and cyclohexane?
Water - 78.54
Ethanol - 24.30
Cyclohexane - 2.01 (not polar)
What is the difference between molarity and molality? Why is molality used?
Molarity: moles per volume of solution
Molality: moles per mass of solvent
Molarity depends on temperature (because volume depends on temperature), molality avoids this
What is the equation for mole fraction?
mole fraction of solute B = xB = nB/(nA + nB)
Number of moles of the solute over the total number of moles of a solution
What is the vapour pressure?
This is the pressure of the gas inside a container if liquid is inserted into a sealed container which previously held a vacuum. Over time molecules will evaporate and condensate from the liquid leading to a lack of vacuum, it is this pressure that is measured.
What is the partial pressure?
This is the vapour pressure of the solvent or solute when a solution is added to a sealed container holding a vacuum. The total pressure is the sum of the partial pressures of the solute (B) and solvent (A)
What is Raoult’s law? Which solutions is Raoult’s law most true for?
PA = PA* . xA
PA = partial pressure of solvent A PA* = vapour pressure of pure A xA = mole fraction of A
Most true for ideal solutions
How would an ideal solution be identified?
Plotting a graph of paRTIAL PRESSURE AGAINST MOLE FRACTION, if ideal then the lines will be straight.
P = PA + PB
Do non-ideal solutions obey Raoult’s law?
nope - if you plot partial pressure against mole fraction the lines would be curvy
At what point do non-ideal solutions follow Raoult’s Law?
When the mole fraction of the solute (B) is small - aka when the solution is almost pure solute. In this case, most of the acetone molecules can only see other acetone molecules so solution behaves ideally.
What type of behaviour is described by Henry’s law? What is the equation?
The linear variation of solute partial pressure at low mole fractions (of solute)
PB = KB . xB
PB = partial pressure of solute B KB = experimentally determined parameter xB = mole fraction of solute B
What is the difference between Henry’s and Raoult’s law?
Henry’s law does not use the pure liquid (solvent A) vapour pressure as the constant, instead it uses an experimentally determined quantity
What is an ideal-dilute solution?
Very dilute solution in which solvent (A) obeys Raoult’s and solute (B) obeys Henry’s law.
What is the impact of Henry’s law on biology?
Important in determining implications for respiration under abnormal pressures (e.g. diving, climbing) - as need to know how gases are exchanged between blood/air in alveoli
At what concentration of solute may electrolyte solutions show some form of ideality?
0.001 moldm-3
How may an electrolyte solution be formed?
Dissolution of an ionic species such as NaCl
Why do macromolecule solutions exhibit strongly non-ideal characteristics?
Due to their bulk - large numbers of solvent molecules are stuck on the surfaces of the macromolecules which affect the entropy of the solvent (among other thermodynamic properties). The solvent molecules solvate onto the outside also increased the drag of the macromolecules increasing the viscosity.
What is enthalpy and what is the equation for it?
Enthalpy is the heat content
Enthalpy change is the heat flow into a system at constant pressure
H = U + pV
H = enthalpy U = internal energy p = pressure V = volume
What is entropy and what is the equation for it?
A measure of how evenly energy is distributed in a system (state of disorder of a system)
S = k.lnW
S = entropy k = Boltzmann constant W = multiplicity -
What is the second law of thermodynamics?
A system with constant volume and internal energy will adopt a configuration that maximises it’s entropy
What does entropy require?
A particular direction for time (arrow of time)
What is Gibbs free energy?
The maximum amount of energy available in a system to do non-expansion work under conditions of constant temperature and pressure
aka in a biological system this tells us how much energy is available to do biological work
Define temperature
A measure of how much the internal energy changes when the entropy is varied and volume held constant BUT thats a bit intense so
amount of kinetic energy of the molecules in the system
What is the heat capacity (Cv/Cp)? What are the equations for this?
A measure of how much internal energy/enthalpy changes as the temperature is varied. Equations are approximately equal not completely.
Cv (constant volume) = deltaU/deltaT
Cp (constant pressure) = deltaH/deltaT
U = internal energy T = temperature H = enthalpy
What is another equation for the heat capacity Cp?
C = q/deltaT
q = heat supplied to the system
Why are the heat capacity equations only approximately equal?
There are assumptions made about the nature of heat transfers and unchanging nature of C with T