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what is electrochemistry
an analytical technique that measures ion in solution by electrical properties
what are most commonly measured ions?
sodium (Na+)
potassium (K+)
chloride (Cl-)
bicarbonate (HCo3-)
calcium (Ca+2)
magnesium (Mg+2)
what other non-ionic analytes does electrochemistry also measure?
oxygen or BUN
what does Ohm’s Law describe?
the relationship between electrical potential (E), current (I), and resistance (R)
what is the relationship between E and I in Omh’s law?
directly proportional (increase of E and Increase of I)
if 2 are constant then the 3rd one is measured (R)
which is the most common electrochemical method?
potentiometry
what is potentiometry
measures electrial potential in volts
what is the standard units of potentiometry?
volts
what is conductivity?
combined ability of ion to carry a charge
what is coulometry
measures the flow of electrial charge per unit of time in coulombs
what is the standard unit of coulometry
coulombs
what is amperometry?
meausre current in amperes
what is the standard units of amperometry?
amperes
what is polarography
measures current while controlling an increase in voltage
what is voltammetry?
measures the current at an electrode using a specific voltage generated at another (opposite) electrode
what is osmometry?
measuring dissolved particles in a solution using a series of variable resisters
what is an example of osmometry?
osmolality using the freezing point depression
what is the principle of potentiometry?
is an electrical system in which change in electrical potential is measured between a detecting electrode and standard reference electrode which the current is kept constant
what is detecting electrode?
aka indictor electrode
measures patient’s potential
what is standard reference electrode?
is the known value
the detecting electrode is compared to
what are used to measure the activity of one ion vs the other ion in potentiometry?
ion-selective electrodes
what are electrodes made up of?
made up of materials that are more selective for one ion compared to other similar ions
how is voltage changed measured and what does it reflect in potentiometry?
measured when ion comes in contact with electrode and reflection of the ionic activity
what are ion-selective electrodes (ISE)?
contains a selective membrane or layer that interacts with one particular ion more than others, making it specific to that ion
what is electrical potential set up with?
with a reference elctrode to which a standard voltage is applied and current kept constant
what is the change in potential due to?
due to the presence of ions in the solution
what is a “salt bridge”?
is a circuit between the two electrodes is completed by a liquid junction
what is ISE and reference sample is connected by?
salt bridge (potentiometer)
what is the ISE for SODIUM?
glass membrane
made up of: lithium aluminum silicate or silicon dioxide contained ionophore like monesin (antibiotic)
what is the ISE for POTASSIUM?
liquid membrane
contains: valinomycin (antibiotic)
what is ISE for CO2/HCO3-?
2 membrane separated by buffer
outer: gas permeable
inner: glass membrane
made up of silicon dioxide/lithium and calcium oxide glass
how does the ISE of Co2/HCO3- work?
once diffusion occurs, gass reacts with buffer to produce H+ whichis proportional to total CO2 in plasma
H+ ions are then detected by the glass membrane of silicon dioxide/lithium and calcium oxide glass that is selective for H+
what is the ISE for CLORIDE?
solid-state membrane
contain: silver chloride
what is ISE for CALCIUM?
membrane made up of PVC
contain: neutral liquid carrier (gel)
what 2 ways can ISE measured?
directly and indirectly
what is the direct measurement of ISE?
measures electrolytes in undiluted samples?
what is direct measurement NOT SUBJECTED TO?
measurement of Na
what is indirectly measurement of ISE?
measures electrolytes by diluting the sample with diluent prior to analysis with the electrode
what is the dilutional effect of sodium?
an increase of lipids or protein in liquid space causes less space in sample causing a falsely decrease value
what specimens can be used in ISE?
venous serum or lithium heparin whole blood or plasma.
what is the preferred speciment of ISE
heparinized plasma
b/c less potassium than serum due to platelet release during coagulation
what speciment should be avoided?
hemolysis
due to K+ intracellular causing false increase
fist clenching, leakage from RBCs
what other specimen can be used?
urine, sweat, CSF, gastric fluid but have short stability
what causes a false decrease in ISE?
protein build up on the surface of the electrolyte membrane
what causes a false decrease in NA and CL in indirect ISE systems?
dilutional effected caused by increase lipid and protein levels.
these high amounts displace some of the volume of plasma within the dilution
what are the solutions to the dilutional effect of Na and Cl?
drawing a fasting sample (less triglyerides)
ultracentrifugation (faster, spins component to bottom)
use direct method (instrument based)
what is the principle of conductivity?
is the combined ability of all ions in a solution to conduct or carry an electrical charge
what does the alternating current do in conductivity?
is applied to electrodes that generates the electrical potential in order to prevent polarization of electrodes
how does alternating current relate to the relationship of conductivity and resistance?
allows them to be reciprocal of each other
higher conductivity = lower resistance
what is Ohmic material?
follow Ohm’s law
E= I x R
what is conductivity used to measure?
total CO2 measurement
what are pH meters used for?
adjusting pH of reagents
determine pH of clinically significant body fiulds
what is the principle of amperometry?
a fixed potenial is applied to a electrochemical cell
the applied potential permits some compounds in the sample that come into contact with the elelctrodes to be oxidized or reduced
what does the potential serve as in amperometry?
generating or exictation signal
the reponse is the current measured
what is the most common electrol in amperometry?
Clark PO2
what does Clark PO2 electrode contains?
gas-permeable membrane
allows dissolved oxygen to pass through
what does the membrane of Clark PO2 prevent?
prevents other blood constituents from pass through that may inter fere with the electrode
what happens after oxygen passes through the Clark PO2 membrane?
mixes with a phosphate buffer solution and reacts witha polarized platinum cathode
what does the cathode have?
has an applied voltage which results in the reduction of oxygen
what does the reduction of oxygen produce?
flow of electrons (electrial current) and magnitude of current is proportional to the amount of oxygen present
what is the principle of coulometry?
uses the measurement of coulombs, flow of electrons per unit of time
coulometric tiration
what is titration?
a process of determining an unknown concentration of a substance by reacting it with an equivalent concentration of a known substance
what electrolyte is most commonly measured with columetry?
chloride
what does coulometry use to measure with?
silver anode that release silver ions at a constant rate due to constant electrical potential
what do silver ion react with? and what do they form?
reacts with chloride ions
forms insoluble silver cloride
what happens when all the chloride ions reacted with the generated silver ions?
causes a sharp increase in current conducted
how is current related to the cloride activity?
current relates to electrical charge per unit of time, time of titration proportional to the chloride activity
what analysis is coulometry most commonly used for?
sweat cloride analysis (CF testing in peds pt)
what is another name for voltammetry?
anodic stripping voltammetry
what is the principle of voltammetry?
electrochemical technique that involves electrical portential that varied over time
what is step 1 of voltammetry?
at the reference electode, a direct current is applied initially and large negative portenttial is generated
what are being reduced at the sruface of the reference lectrode? and causes what?
metal ions
causes them to be strongle attracted to surface of electrode
what is step 2 of voltammetry?
the direct current is then applied as a large linear postiive potential causing the metal ions to be gradually reoxidized and stripped from the electrode in teh order of the characcterisitic potential
what records current vs applied ptoential to quantify the substance present in voltammetry?
microammeter
what is polarography?
type of voltammetry
potential is applied constantly and slowly increased
causes reduction to occur which results in the electrical current to be proportional to the amount present.