(CSMLS) ELECTROCHEMISTY & ELECTROLYTES Flashcards
(46 cards)
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
Causes of decreased anion gap
- hypoalbuminemia (primary unmeasured anion)
- increased cations; hypercalcemia and hypermagnesemia
- hypergammaglobulinemia; paraproteins (ie. IgG) have a positive charge
- laboratory error
How is sodium regulated ?
By the kidneys and renin angiotensin aldosterone system:
- DROP IN BLOOD PRESSURE AND FLUIDS causes kidneys to release renin
- liver releases angiotensin = activated by renin
- angiotensin II stimulates adrenal grand to release aldosterone
- aldosterone = KIDNEYS REABSORB SALT and WATER
How is chloride regulated ?
- by the kidney and the renin angiotensin aldosterone system (same as sodium)
- excess chloride is excreted in sweat and urine
How is potassium regulated ?
By the kidney, aldosterone and insulin
How is bicarbonate regulated ?
The kidneys and lungs regulate bicarbonate and CO2 levels
What is metabolic alkalosis associated with ?
Increase in bicarbonate