Block 5 - Acids and Bases Flashcards
Brønsted acid
A substance that has a proton (H+) which can be taken by a base
Any molecule that contains H joined to a more electronegative atom
Brønsted base
A substance that can take a proton from an acid
Has a lone pair of electrons
Amphoteric species
Species that act as both acids and bases
e.g. H2O, H2PO4
Diprotic, tripotic acids
Some acids can give up more than one proton, where removal of each proton is a distinct step
Conjugate base
The species left behind after the Brønsted acid has transferred a proton
Conjugate acid
The species produced when the Brønsted base accepts a proton
Equilibrium constant (Kw)
Kw = [H3O+][OH-] = 10^-14
What does Kw depend on
Temperature dependant
Since auto-ionisation of water is endothermic, Kw increases with temperature
What is ‘p’
A short-hand for -log10
pH < 7, pH = 7, pH > 7
pH < 7 = acidic
pH = 7 = neutral
pH > 7 = basic
pH < 0
pH can be less than 0, but rare and only happens if solution is highly acidic
Strong acid
Where equilibrium lies far to the right
Uses full arrow (–>)
Weak acid
Equilibrium arrow used
Strong and weak acids - concentration
Definition of strong and weak acids is independent of concentration
Proton transfer reactions - speed
Fast, so acid-base systems reach equilibrium rapidly
Strong and weak acids - equilibrium
Strong acid: equilibrium lies far to the right
Weak acid: equilibrium lies more to the left
Ka
Known as acidity constant, acid dissociation constant, acid ionisation constant
Strength of acid - Ka
Large value of Ka –> more reaction lies to right –> stronger acid
Strength of acid - pKa
Smaller pKa –> stronger acid
Strong acid and strong base - pKa
Strong acid: pKa < 0
Strong base: pKa > 14
As an acid gets weaker…
Its conjugate base gets stronger
Bonds are strongest when…
They are short (joined atoms are close together) and electron density between the two joined atoms is large
What affects acidity (strength of acid)
More positive or negative charge
Charge stabilisation:
- Inductive effects
- Delocalisation
Acidity - positive and negative charges
It’s easier for a positively charged molecule to lose a positively charged proton
Ease of proton transfer decreases as charge on molecule becomes more negative
Acidity - charge stabilisation by inductive effects
Presence of nearby electronegative atoms / EWGs move charge away from acidic H –> -H bonds weaker –> stronger acid
Acidity - charge stabilisation by delocalisation
Allows charge to be spread out over a large number of atoms
Can occur through resonance
To make a stronger acid…
Make the conjugate base as stable as possible
Relationship between pKa and pH
pH < pKa : more acid form (HA)
pH = pKa : HA and A- in equal conc
pH > pKa : more base form (A-)
Di/tri-protic acids - pKa
Have 2 (or 3 respectively) pKa values - one for loss of first proton, and one for loss of second pKa increases (i.e. pKa1 < pKa2)
Amino acids - general structure
NH2CHRCO2H
where R defines the amino acid
Amino acids - groups
Amine group: -NH2 (conjugate acid -NH3+)
Carboxyl group: -CO2H (conjugate base -CO2-)
Isoelectric point
The point at which the zwitterion for amino acids has max conc
Amino acids - electrophoresis
Allows separation of mixtures of amino acids by their charge
How many species exist at one point in time
For acids and bases, the normal situation is that a max of two species exist significantly in any conditions
When will both species of a conjugate acid/base pair be present
Within 1 pH unit (+/- 1) of the pKa of the acid form
Amino acids - pKa
If pH < pKa, exists as acidic form (NH3 or COOH)
If pH > pKa, exists as basic form (NH2 or COO-)
If pH = pKa, exists as acidic and basic form (mixture)
Strong acid calculations - assumption(s)
Only the strong acid contributes to [H3O+]
This is not true if pH > 6
Strong base calculations - assumption(s)
Only the strong base contributes to [OH-]
This is not true if pH < 8
Predicting pH of weak acids
Weak acid –> doesn’t dissociate to large extent –> dominant species is acid form –> pH < pKa
Weak acid calculations - assumption(s)
- The only source of H3O+ is from the dissociation, so [conjugate base] = [H3O+]
- The dissociation is small compared to the original amount, so
[HA] = [HA]0 - [conjugate base] ≈ [HA]0
Weak acid calculations - checking assumptions
- pH more than 1 below 7
- pH more than 1 below pKa
- Check pH is on acid side of pKa: pH < pKa
Predicting pH of weak bases
Weak base –> base form dominates –> pH > pKa
Weak base calculations - assumption(s)
- The only source of OH- is from the reaction, so
[conjugate acid] = [OH-] - The amount of reaction is small compared to the original amount, so
[base] = [base]0 - [conjugate acid] ≈ [base]0
Weak base calculations - checking assumptions
- pH is more than 1 above 7
- pH is more than 1 above pKa
- pH is on base side of pKa: pH > pKa
Amphoteric species calculations - determining which pKa are involved and predicting
Relevant ones where species of interest is involved in equation
Expect pH between pKas of relevant equations
Amphoteric species calculations - assumption(s)
[H3O+] and [OH-] are much less than the conc of the amphoteric species, so the only reaction the amphoteric species undergoes is with itself
Amphoteric species calculations - checking assumption
[H3O+] «_space;original conc
Buffer solutions: Henderson-Hasselbach equation - assumption(s)
Can only use for buffers!!
Extent of dissociation of weak acid and its conjugate base is small, so
[HA] = [HA]initial and
[A-] = [A-]initial
When HA and A- are of similar conc, the log term is small and pH is approx equal to pKa and will only change by +/- unit
Buffer solution
Solution where pH changes much less than that of pure water when acid or base is added, i.e. resists changes in pH
Typically contain either equal amounts of a weak acid and its conjugate base (where buffer pH < 7) or equal amounts of a weak base and its conjugate acid (where buffer pH > 7)
How does a buffer work
It contains both species that can accept protons (to react with added acids) and that can donate protons (to react with added base)
When does a buffer solution work best
When [HA] is close to [A-], i.e. most suitable at pH around pKa of the acid
More effective with higher conc of the two species as there is more to react with added acid or base
When a buffer is fully used up…
It has exceeded its capacity, and pH will change significantly
pH of unbuffered solution - addition of acid or base
pH changes significantly
pH of unbuffered solution - dilution
pH changes significantly
pH of buffer system - dilution
Doesn’t change (much)
pH of buffer system - addition of acid or base
pH of solution changes by a small amount
Titration
A method of volumetric analysis for determining conc of an unknown solution by letting it react with another whose conc is known
Titration - equivalence point
Volume at which the reaction is just completed
Titration of strong base with strong acid
Before any acid is added, pH is high
As acid is added, pH of solution falls, gradually at first, then faster as equivalence point is approached
After EP, rate of pH change slows
Well beyond the EP, pH is low
Since acid and base are strong, both 100% dissociated and pH at EP is 7
Titration of weak acid/base with strong base/acid - exact pH of EP depends on…
pKa of acid
Titration of weak acid with strong base
Beginning of titration, weak acid only
pH rises fairly steeply when first drops of base are added - only little OH- required to react with free H3O+
Buffer region - pH changes slowly
Half-equivalence point - reaction is half complete, so there are equal amounts of acid and base present
Equivalence point - reaction is 100% complete, only conjugate base present –> pH > 7
After EP when all acid has been deprotonated, solution is essentially a strong base and curve flattens out; pH determined by strong base
Titration - half-equivalence point
pH = pKa
Can only work out pKa for weak acid/base involved in titration, not strong acid/base, as no equilibrium between conjugate acid and base for strong acids/bases so at 1/2 equivalence point, pH only determined by amount of unreacted acid present, not due to an equilibrium
Titration of weak base with strong acid
Beginning of titration - weak base only
Buffer region - pH changes slowly
Half-equivalence point - reaction is half complete, so there are equal amounts of acid and base present
Equivalence point - reaction is 100% complete; only conjugate acid present; pH < 7
After EP when all base has been protonated, solution is strong acid and curve flattens out; pH determined by strong acid
End point
When we decide to stop, generally because observable change has occurred
Ideally, end point is at equivalence point
Indicators
Compounds that are diff colours in their acid and base forms, i.e. they are acids or bases too
Colour change occurs around at pH around pK(In)
pK(In) should be around 1 pH unit of pH of equivalence point
Titration curves for polyprotic acids
Multiple equivalence points and buffer regions