physical chemistry Flashcards
definition of chemical equilibrium
when composition of the reactants and products remains constant indefinitely
what does the value of K indicate?
position of equilibrium
what is given a value of 1 at equilibrium?
concentrations of pure solids and pure liquids (water)
what is the one factor which affects K value?
temperature
effect of increasing temperature on K value
exothermic reactions - decrease in K
endothermic reactions - increase in K
meaning of different K values (>/<1)
> 1 = equilibrium lies to right
<1 = equilibrium lies to left
effects of a catalyst on equilibrium
- no effect on position
- increases rate of forward and reverse reactions equally
- no change to K value
- equilibrium reached more quickly
dissociation of strong acids
dissociates fully into its ions, equilibrium lies almost fully to the right
dissociation of weak acids
dissociates partially into its ions, equilibrium lies almost fully to the left
examples of strong acids
hydrochloric, sulfuric, nitric
examples of weak acids
carboxylic, sulphurous, carbonic
examples of strong bases
group 1&2 metal hydroxides (except magnesium)
examples of weak bases
ammonia, ammines
Bronstead & Lowry definitions of acids and bases
acids donate protons, bases accept protons
what’s a conjugate base?
substance left over when an acid donates a proton (what acid becomes)
what’s a conjugate acid?
substance made when a base accepts a proton (what base becomes)
what does amphoteric mean?
acts as both an acid and a base e.g water
what is a buffer solution?
solution where the pH will remain approximately constant when a small amount of acid, alkali or water is added.
often used to calibrate pH meters.
what are acidic buffers made of?
a weak acid and the salt of that acid
what are basic buffers made of?
a weak base and the salt of that base
what are indicators?
weak acids which change colour depending on the pH of the solution
why does the colour change in the presence of an indicator?
equilibrium shifts
selecting indicator based on acid/base combo
both strong: indicator must change colour around pH 7
strong acid/weak base: indicator must change colour around pH 5
weak acid/strong base: indicator must change colour around pH 9
enthalpy definition
energy stored in chemical bonds
enthalpy of formation definition
enthalpy change when one mole of a substance is prepared from its constituent elements in their standard states.
entropy definition
the measure of the disorder in a system
states and entropy
gaseous substances have greater entropy than liquid ones, liquid substances have greater entropy than solid ones
ways to increase entropy
- increase temperature
- break a large molecule down into smaller ones
how to calculate entropy
take away entropy of reactants from that of the products
what does negative entropy mean?
decreased entropy = reaction becoming more ordered
relationship between enthalpy and entropy
if enthalpy is positive, so is entropy, and vice versa
first law of thermodynamics
energy cannot be created or destroyed, only changed from one form to another
second law of thermodynamics
the total entropy of a reaction system and its surroundings always increases for a spontaneous reaction
third law of thermodynamics
the entropy of a perfect crystal at 0K is zero as particles have no kinetic energy.
exo/endo and entropy
exothermic reactions increase the entropy of the surroundings.
endothermic reactions decrease the entropy of the surroundings
Gibbs free energy for spontaneous reactions
Gibbs energy must be negative for a reaction to be spontaneous (feasible)
feasible reactions?
tend towards products rather than reactants
Gibbs energy at equilibrium?
- zero
- a reaction will proceed spontaneously until the conformation is reached where ^G=0
entropy changes and feasibility
if entropy change is negative, then anything below T is feasible.
if entropy change is positive, anything above T is feasible.
what does first order mean?
when concentration of reactant doubles, so does rate of reaction
what does second order mean?
when concentration doubles, rate of reaction quadruples.
what does 0 order mean?
changing concentration of reactant has no effect on rate of reaction
how to find overall order
add orders of each reactant together
what is rate determining step?
slower step in reaction mechanism