UV-Vis Spectroscopy Flashcards

1
Q

The electromagnetic Spectrum

HIGH Frequency(v), HIGH Energy
|
V
LOW Frequency(v), LOW Energy

A

X-RAY

UV

INFRARED

MICROWAVE

RADIO

FREQUENCY

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2
Q

___ has many different applications in ORGANIC and BIOLOGICAL CHEMISTRY

Most basic of these application is the use of the ___ to deptermine the concentration of a ___.

A

UV-Vis Spectroscopy

Beer-Lambert Law

Chromophore

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3
Q

Part of the molecule where the ABSORPTION occurs and where the main change of the geometry or electron density, etc. appears after the excitation process.

A

Chromophore

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4
Q

The ___ is the application of the observation that, within CERTAIN RANGES, the ABSORBANCE of a chromophore at a given WAVELENGTH VARIES in a linear fashion with its CONCENTRATION

TLDR; HIGHER CONCENTRATION, GREATER ABSORBANCE

Is what makes SPECTROPHOTOMETRIC DETERMINATION of ORGANIC COMPOUNDS feasible

A

Beer-Lambert Law

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5
Q

True or False: Inorganic species cannot absorb

A

FALSE, a number of inorganic species can absorb

many IONS of the TRANSITION METALS are COLORED in solution and can thus be determined by spectrophotometric measurement.

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6
Q

SPECIES that show CHARACTERISTIC ABSORPTION BANDS (6)

A

NitrITE

NitrATE

Chromate IONS

OXIDES of NITROGEN

Halogens

Ozone

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7
Q

___ can be determined photometrically by causing them to react with ___ to produce products that ABSOR STRONGLY in UV and VISIBLE regions.

A

non-absorbing analytes

chromophoric reagents

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8
Q

The successful application of these COLOR-FORMING REAGENTS usually requires that their REACTION with the ANALYTE be forced to ___ unless they use methods such as KINETIC methods.

A

NEAR COMPLETION

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9
Q

Typical INORGANIC REAGENTS for NON ABSORBING:

Thiocyanate ion for (3)

A

Iron

Cobalt

Molybdenum

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10
Q

Typical INORGANIC REAGENTS for NON ABSORBING:

Hydrogen Peroxide for (3)

A

Titanium

Vanadium

Chromium

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11
Q

Typical INORGANIC REAGENTS for NON ABSORBING:

Iodide ion for (3)

A

Bismuth

Palladium

Tellurium

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12
Q

____ that FORM STABLE COLORED COMPLEXES WITH CATIONS are even more important.

A

Organic chelating reagents

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13
Q

Common examples for ORGANIC CHELATING REAGENTS for NON ABSORBING:

Copper

Lead

Iron

Nickel

A

Common examples for ORGANIC CHELATING REAGENTS for NON ABSORBING:

Copper - Diethyldithiocarbamate

Lead - Diphenylthiocarbazone

Iron - 1,10 Phenanthroline

Nickel - Dimethylglyoxime

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14
Q

particularly important for quantitative analysis because MOLAR ABSORPTIVITIES are unusually LARGE

(e > 10,000 L mol-1 cm-1 ), which leads to HIGH SENSITIVITY.

Many INORGANIC and ORGANIC complexes exhibit this TYPE OF ABSORPTION and are therefore called ____

consists of an ___ bonded to an ___

A

charge-transfer complexes

electron-donor group, electron acceptor

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15
Q

When a CHANGE-TRANSFER COMPLEX absorbs radiation, an ____ from the DONOR is transferred to the ____ that is largely associated with the ACCEPTOR.

The EXCITED STATE is this the product of a kind of INTERNAL ___ / ___ process

This behavior DIFFERS FROM ORGANIC CHROMOPHORE in which the excited electron is in a molecular orbital that is shared by ___.

A

Electron , Orbital

Oxidation / Reduction

two or more atoms

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16
Q

TYPICAL INSTRUMENTS:

use a FILTER FOR WAVELENGTH SELECTION in conjunction with a suitable RADIATION TRANSDUCER (converts a signal or light into a current or voltage).

have the advantages of SIMPLICITY, RUGGEDNESS, and LOW COST; most often used for the ___; good signal-to-noise ratio.

find considerable use as detectors for chromatography, electrophoresis, immunoassays, or continuous flow analysis.

A

Photometers

VISIBLE REGION

17
Q

Offer the considerable advantage that the WAVELENGTH USED CAN BE VARIED CONTINUOUSLY, making it possible to record ____

cover the ___ and occasionally the ___region

A

Spectrophotometers

Absorption Spectra

UV/visible , near-infrared

18
Q

TO FIND IDENTITY of the absorbing groups by COMPARING the spectrum of an ANALYTE with those of ___ containing various ___.

A

SIMPLE MOLECULES

chromophoric groups

19
Q

TRUE or FALSE: ultraviolet spectra have sufficient fine structure to permit an analyte to be identified

A

FALSE, ultraviolet spectra do not have sufficient fine structure to permit an analyte to be identified unambiguously.

ultraviolet qualitative data must be supplemented

20
Q

Evidence that supplements UV qualitative data: (6)

A

Infrared

Nuclear Magnetic Resonance

Mass Spectra

Solubility

Melting

Boiling point

21
Q

Important characteristics of SPECTROPHOTOMETRIC and PHOTOMETRIC methods

A

Wide applicability

High Sensitivity

Moderate to High Selectivity

Good Accuracy

Ease and Convenience

22
Q

WIDE APPLICABILITY:

Nonabsorbing species can also be determined after ____ .

Large majority of determinations performed in clinical laboratories

A

chemical conversion to absorbing derivatives

23
Q

HIGH SENSITIVITY:

TYPICAL DETECTION LIMITS for absorption spectroscopy range from ___; can be extended to ___ with procedural modifications.

A

10^-4 to 10^-5 M

10^-6 or even 10^-7 M

24
Q

MODERATE TO HIGH SELECTIVITY:

Often a WAVELENGTH can be found at which THE ANALYTE ALONE ABSORBS

HOWEVER, ___ DO OCCUR, corrections based on ADDITIONAL MEASUREMENTS AT OTHER WAVELENGTHS sometimes ELIMINATE THE NEED for a separation step.

When SEPARATIONS are required, spectrophotometry often DETECTS THE SEPARATED SPECIES

A

Overlapping Absorption bands

25
Q

GOOD ACCURACY:

The relative errors in concentration encountered lie in the range from ___. Such errors can often be decreased to a FEW TENTHS OF A PERCENT W/ SPECIAL PRECAUTIONS

A

1% to 5%

26
Q

PROCEDURAL DETAILS: (6)

A

(a) Wavelength Selection.

(b) Variables That Influence Absorption.

(c) The Relationship between Absorbance and Concentration

(d) The Standard Addition Method.

(e) Analysis of Mixtures.

(f) Photometric and Spectrophotometric Titrations

27
Q

(a) Wavelength Selection.

For MAXIMUM SENSITIVITY, spectrophotometric absorbance measurements are usually made at the ____ because the ____ is greatest at this
point.

In addition, the ABSORPTION CURVE is often ___ at a maximum, leading to good adherence to BEER’S LAW and less uncertainty from failure to reproduce precisely the wavelength setting of the instrument.

A

wavelength of maximum absorption

change in absorbance per unit of concentration

flat

28
Q

(b) Variables That Influence Absorption.

The effects of these 5 variables must be known so absorbance will not be materially affected

A

 nature of the SOLVENT,
 the pH of the solution,
 the TEMPERATURE,
 high ELECTROLYTE concentrations,
 the presence of INTERFERING SUBSTANCES.

29
Q

(c) The Relationship between Absorbance and Concentration.

CALIBRATION STANDARDS should approximate as closely as possible the OVERALL COMPOSITION OF THE ACTUAL SAMPLES and encompass a reasonable range of analyte concentrations.

CALIBRATION CURVE is usuallly ABSORVANCE BERSUS CONCENTRATION OF SEVERAL STANDARDS to evaluate the relationship.

HOWEVER, only a SINGLE STANDARD is used to determine ___.

Unless there is no other choice, it is NEVER GOOD to base the results of a determination solely on a ____ for the (answer above).

A

Molar absorptivity

literature value

30
Q

When two or more compounds do not chromatographically separate

A

Co-eluting

31
Q

(d) The Standard Addition Method.

Used when ___ are a problem due to co-eluting compounds. It usually improves results by providing compensation for these effects.

For example, the ABSORBANCE of many ___ is DECREASED in the presence of ___ and ___ because of the tendency of these ANIONS FORM COLORLESS COMPLEXES WITH METAL IONS (the color formation
reaction is often LESS COMPLETE, thus sample ABSORBANCE LOWERED).

Ideally, the composition of calibration standards should approximate the composition of the samples to be analyzed (NOT ONLY FOR ANALYTE CONCENTRATION but also CONCENTRATION OF THE OTHER SPECIES IN THE SAMPLE MATRIX)

A

Matrix effects

Colored complexes of metal ions

sulfate , phosphate ions

32
Q

(e) Analysis of Mixtures.
 The TOTAL ABSORBANCE OF A SOLUTION at any givenwavelength is equal to the ___ in the solution.

 This occurs completely even with spectra overlap.

A

sum of the absorbances of the INDIVIDUAL COMPONENTS

33
Q

F. Photometric and Spectrophotometric Titrations

 useful for locating the ___ of titrations.
 requires one or more of the reactants or products ___ or that an ___ be added to the analyte solution.

A

equivalence points

absorb radiation

absorbing indicator

34
Q

TITRATION URVES of a PHOTOMETRIC TITRATION

 plot of absorbance (corrected for volume change) as a function of titrant volume.
 If conditions are chosen properly, the curve consists of___,

◼ one occurring ___ of the
titration
◼ the other located ___ region.

The end END POINT is taken as the INTERSECTION of extrapolated linear portions of the two lines.

A

two straight-line regions with different slopes

prior to the equivalence point

well beyond the equivalence-point