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pH
Buffered solution
Depend on ratio salt/acid Depend on concentration salt + acid Depend on amount of added a, b
Acid
a substance which donates a proton (or hydrogen ion) the addition of an acid to water will increase hydrogen ion concentration (more than 10-7 mol/l)
Base
a substance that accepts protons the addition of a base will decrease the concentration of hydrogen ions.
dissociation of water
The dissociation of water can be represented by: H2O H+ + OH In pure water the concentrations of H+ and OH- ions are equal and at 25C both have the values of 1 x 10-7 mol/l.
dissociation of water
The hydrogen ion concentration range is from 1 mol/l for a strong acid down to 1 x 10-14 mol/l for a strong base. To avoid the use of such low values pH has been introduced as a more convenient measure of hydrogen ion concentration.
pH scale
pH
the negative logarithm of the hydrogen Ion concentration [H+]
pH = -log10 [H+]
pH
pH of a neutral solution like pure water is 7, why? because the conc. of H+ ions (and OH- ) ions = 1 x 10-7 mol/l
pH
pHs of acidic solutions will be less than 7 pHs of alkaline solutions will be greater than 7
Affect the solubilities of drugs that are weak acids or bases Affect the stabilities of many drugs Affect the ease of absorption of drugs from the GIT
Solution properties
Buffer solution
significance
In solutions of weak acids or weak bases equilibria exist between undissociated molecules and their ions.
HA
H+ + A -
Such equilibrium do not occur in solutions of strong acids or bases in water, why?
The ionization constant (dissociation constant) Ka of a weak acid can be obtained by applying the Law of Mass Action: Ka = [H+] [A-] [HA]
pKa = the negative logarithm of Ka pH = the negative logarithm of the hydrogen ion conc. [H+] [HA] pKa = pH + log [A-]
Henderson-Hasselbalch equation: A general equation that is applicable to any acidic drug with one ionizable group where: Cu = conc. of the unionized ; Ci = conc. of the ionized species Cu
The ionization constant (dissociation constant) Ka of a protonated weak base is given by Ka = [H+] [B] [BH+]
Taking the negative log of this equation: [BH+] pKa = pH + log [B]
Henderson-Hasselbalch equation: A general equation that is applicable to any weak basic drug with one ionizable group where: Ci = conc. of protonated ; Cu = conc. of the unionized species pK = pH + log Ci
The degree of ionization of a drug in a solution can be calculated from the Henderson-Hasselbalch equations for weak acids and bases if the pKa of the drug and the pH of the solution are known Such calculations are useful in determining the degree of ionization of drugs in various parts of the GIT and in the plasma Examples 1. The pKa of the weakly acidic drug sulphapyridine is about 8.0 and if the pH of the intestinal contents is 5.0 then the ratio of unionized:ionized drug is given by: Cu pKa - pH = 8 5 = 3 Ci C :C = antilog 3 = 103 : 1
log =
The pKa value of aspirin, which is a weak acid, is about 3.5, and the pH of the gastric contents is 2.0 log = Cu pKa - pH = 3.5 - 2.0 = 1.5
Ci the ratio of the conc. of unionized acetylsalicyclic acid to acetylsalicylate anion is given by: Cu:Ci = antilog 1.5 = 31.62 :1 The pH of plasma is 7.4 so that the ratio of unionized:ionized aspirin in this medium is given by: log Cu Ci = pKa - pH = 3.5 7.4 = -3.9
Solution properties
Buffer solution
significance
Buffered Solutions
A buffered solution or buffer is a solution that resists a change in pH upon addition of small amounts of strong acid or strong base.
Composition and Action of Buffered Solutions A buffer consists of a mixture of a weak acid (HX) and its conjugate base (X). HX(aq) H+(aq) + X(aq) Thus a buffer contains both: An acidic species (to neutralize OH ) and A basic species (to neutralize H +).
Buffer Capacity
A buffer counteracts the change in pH of a solution upon the addition of a strong acid, a strong base, or other agents that tend to alter the hydrogen ion concentration. Buffer capacity : buffer efficiency, buffer index or buffer value Is the resistance of a buffer to pH changes upon the addition of a strong acid or base. Definition: It can be defined as being equal to the amount of strong acid or strong base , expressed as moles of H +or OH- ions, required to change the pH of one litre of the buffer by one pH unite. Maximum buffer capacity (max) obtain when ratio of acid to salt =
1 i.e. pKa = pH
Definition The ratio of increase of strong base (or acid) to small change in pH brought about by this addition. = B pH
B = the small increment in gram equiv./liter of strong base added to the buffer solution to produce a pH change pH = pH change
:The buffer capacity of the solution has a value of 1 when the addition of 1 gram equiv. of strong base (or acid) to .1 liter of the buffer solution results in a change of 1 pH unit
Ex: Acetate buffer contains: 0.1 mole each of acetic acid & sodium acetate in 1 liter of solution. a) 0.01 mole portions of NaOH is added b) The conc. of Na acetate (the [salt] in buffer equation) by 0.01 mol/l & the conc. of acetic acid [acid] by 0.01 mol/l because each increment of base converts 0.01 mole of acetic acid into 0.01 mole of sodium acetate according to the reaction. HAc + NaOH (0.1 0.01) (0.01) NaAc + H2O (0.1 + 0.01)
The changes in concentration of the salt and the acid by the addition of a base are represented in the buffer equation by using the modified form pH = pKa + log [salt ] + [base] [acid] - [base] Before the addition of the first portion of NaOH, the pH of the buffer solution is pH = 4.76 + log ( 0.1 + 0 ) = 4.76 ( 0.1 0 )
The buffer capacity is not a fixed value for a given buffer system, but depends on the amount of base added. With the addition of more NaOH, the buffer capacity decreases rapidly, and, when sufficient base has been added the acid convert completely into sodium ions and acetate ions The buffer has its greatest capacity before any base is added where [salt] / [acid] = 1, and according to equation, pH = pKa. The buffer capacity is influenced by an increase in the total conc. of the buffer constituents since a greater conc. of salt and acid provides a greater alkaline and acid reserve.
Van Slyke developed a more exact equation for calculation of buffer capacity Ka [H3O+] 2.3 C = ) H3O+])2+ Ka[ C = The total buffer concentration (the sum of the molar ). concentrations of the acid and the salt Ka = dissociation constant H3O+ = hydrogen ion concentration The equation permits the calculation of the buffer capacity at any hydrogen ion concentration, i.e. when no acid or base has been added to the buffer
: Example If hydrogen ion concentration is 1.75 x 10-5, pH = 4.76 what is the capacity of the buffer containing 0.10 mole of ? each of acetic acid and sodium acetate per liter of solution The total concentration , C = [acid] + [salt], is 0.20 mol/l and the dissociation constant Ka is 1.75 x 10-5 Ka [H3O+] 2.3 C = (Ka + [H3O+])2 = 2.3 X 0.20 X (1.75x10-5) X (1.75 X 10-5) = 0.115 [(1.75x10-5) +(1.75 X 10-5)]2
2-The ratio of salt and acid required to produce a pH of 5 was found to be [salt] / [acid] = 1.74/ 1
The buffer capacity equation is used to obtain the total ] 3 ]buffer concentration , C = [salt ] + [acid Ka[H3O+] 2.3 C = ) H3O+])2+ Ka[ )X C X (1.75x10-5) X (1X 10-5 2.3 = 0.02 [(1.75x10-5) + (1 X 10-5)]2 C= 3.75 x 10-2 mol/l From (b): [salt] = 1.74 x [acid], and from (c): C = 1.74 x [acid] + [acid] = 3.75 X 10 -2 mol/l [acid] = 1.37 x 10-2 mol/l [salt] = 1.74 X [acid] = 2.38 X 10-2 mol/l
In summary , the buffer capacity depends on a) the value of the ratio salt/acid , increase as the value( .approaches unity b) the magnitude of the individual concentrations of the ( buffer components, increase as C increased
Solution properties
pH
Buffered solution
Depend on ratio salt/acid Depend on concentration salt + acid Depend on amount of added a, b
I think you are referring to buffers. At the point of half neutralisation, the acid and its conjugate base are at equal concentrations Ka= [H+][A-]/[HA] But when [HA]=[A-] half way through the reacion, this cancels down to Ka=[H+] => pKa=pH
Isoelectric point
The isoelectric point (pI), sometimes abbreviated to IEP, is the pH at which a particular molecule or surface carries no net electrical charge. Amphoteric molecules called zwitterions contain both positive and negative charges depending on the functional groups present in the molecule. The net charge on the molecule is affected by pH of their surrounding environment and can become more positively or negatively charged due to the loss or gain of protons (H+). The pI is pH value at which the molecule carries no electrical charge or the negative and positive charges are equal. The pI value can affect the solubility of a molecule at a given pH. Such molecules have minimum solubility in water or salt solutions at