(CSMLS) ELECTROCHEMISTY & ELECTROLYTES Flashcards
Define “activity” in electrochemsitry
Concentration of an electrolyte measured in an electrochemical cell (used in Nernst equation)
Define “activity coefficient”
Activity of an electrolyte divided by molar concentration
- measurement of the interaction of selected electrolytes with other species in the solution
Define “potentiometry”
Measures electric potential (E) between two electrodes under equilibrium conditions
Components of a potentiometric ion-selective electrode (ISE)
(Ref)erence electrode: stable/ constant potential relative to sample solution
- has a junction (frit) to allow electrical, ionic conductivity (E jxn) between sample and internal chloride sol’n while preventing large convective mixing of sol’ns
(Ind)icator electrode: has an ion selective membrane
- potential occurs when there is a difference in activity of ions on either side of membrane
Physical vs Chemical Properties of an Electrochemical cell
What equation describes the selectivity of an ISE ?
Nicolsky-Eisenman
List 6 general sources of error/ limitations for ISE
- Temperature dependent
- Ionic strength affects activity coefficient
- pH - inadequate conversion of analyte to one form ie. calcium
- Biofouling - protein buildup on membrane
- Cross-reacting ions
- Electrolyte exclusion effect
What is an anion gap ?
The gap between measured cations and anions due to unmeasured anions (proteins, sulphates, phosphates…) and unmeasured cations (calcium, magnesium)
__ is a common reference electrode
Ag/Ag electrode
Normal plasma sample is __% water and _% lipid
Normal plasma sample is 92% water and 8% lipid
Describe pH ISE, including specimen type, and sources of error
glass membrane
ion-exchange along membrane alters electrical potential
change in potential is correlated to H+ activity
Sources of Error:
- temperature dependent; as T increases, pH decreases
- exposure to air decreases CO2 and increases pH
Lipemia plasma sample is __% water and __% lipid
Lipemia plasma sample is 75% water and 25% lipid
What is an ionophore ?
neutral ion carrier
reversibly bind ions at membrane surface while counter-ions remain in solution = electric potential
Eg. valinomycin binds potassium
Describe principle of CO2 ISE
- gas permeable membrane; Teflon or silicon rubber
- CO2 passes membrane and dissolves within inner electrolyte sol’n
- bicarbonate and H+ form
- H+ is detected by interior pH ISE; change in membrane potential is proportional to pCO2
Sources of error for CO2 ISE
- Air exposure decreases [CO2]; false increase in pH
- Biofouling
- Temperature, barometric pressure, incorrect calibration
Sources of error for ISEs
- Fist pumping = increased Ca2+, K+
- Hemolysis = increased K+, phosphorus, Mg+
- Icterus = falsely increased phosphorus
- Lipemia (Na+ falsely decreased in indirect ISE)
Describe the electrolyte exclusion effect
- Exclusion of electrolyte from the fraction of total plasma volume that is occupied by solids
- Electrolytes are accounted for in the water content of sample, not solid
- Sodium concentration is falsely decreased in samples with increased proportions of solids
Causes of increased anion gap
- diabetic ketoacidosis
- lactic acidosis
- renal failure
- renal tubular acidosis
- diarrhea, starvation
- decreased renal tubular reabsorption of bicarbonate
- intoxication (ethanol, methanol, ethylene glycol)
- metabolic alkalosis; proteins gain negative charges = increased unmeasured anions