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150 Cards in this Set

  • Front
  • Back
What are the four steps of chemical analysis
1. For the question
2. Select procedures
3. Sample Prep
4. analysis
What do the following prefixes mean
tera giga mega
tera 10^12, giga 10^9, mega 10^6
what do the following prefixes mean
kilo hecto deca
kilo 10^3 hecto 10 ^2 deca 10^1
What do the following prefixes mean
deci centi milli
deci 1-^-1 centi 10^-2 milli 10^-3
What do the following prefixes mean
micro nano pico femto
micro 10^-6, nano 10^-9, pico 10^-12, femto 10^-15
what is an angstrom
10^-10 meters
What is molarity
moles substance/ L solution
what is formal concentration?
The concentration of a substance if it were not to dissociate. i.e. 1M Acetic acid isn't really 1 molar because its a weak acid and we get some H+ some OAc - and some HOAc. Formal concentration ignores this fact and defines the concentration of this solution as simply 1M
How is % wt. definied
mass solute/mass total solution
how is % volume defined
volume solute/ volume total solution
What is molality
moles solute/ kg solvent
How are ppm and ppb defined
1 ppm= 1g substance/ 1X 10^6 gram solution, 1ppb= 1 g substance/ 1X10^9 gram solution
What is the dilution equation
M1V1=M2V2
Why does boyance affect mass measurements?
The apparent weight of the objects is less than the true weight by an amount equal to the weight of the air displaced by the object
Define each term in the boyance correction equation
m=m'(1-da/dw)/ (1-da/d)`
m is the true weight
m' is the weight read from the balance
da is the density of air
dw is the density of the balance weight
d is the density of the object
When do boyance errors occur during mass measuremetns
A boyancy error will occur when the density of the object is not equal to the density of the calibration weights (if this is the case, the correction factor reduces to 1 and m=m')
If the object is more dense than the calibraiton weights, it will appear to weigh less than its true weight. If the object is less dense than the calibration weight, it will appear to weight more.
Why does temperature effect volumetric measurments
both the liquid being measured and the class expand as the temperature rises. This changes the volume that is acually delivered
What is the calibration equation used for volumetric glassweare
true volume= mass of water X correction factor (ml/g)
How is volumetric glassweare calibrated
A known volume is dispensed and weighed. This mass is multiplied by a correction factor which is simply the density of water at the paticular temperature. This correction gives the volume dispensed.
What are the sig fig rules for log. ie. how many digits shoudl be included in log (339)
The number of digits in the mantissa (the decimal portion of the log) should equal the number of signifiant figures in the original number. So, log 339 would be 2.530 with 3 SFs in the decimal portion
What are the SF rules for antilogs i.e. antilog (-3.42) or 10^-3.42
The number of digits in the decimal portion of the antilog should equal the number of digits in the decimal place of the original number. So, 10^ -3.42 should be written as 3.8 x 10^-4 because there are two digits in the decimal of 3.42
define systematic or determinate error
an error that is repeatable if the measurement is made the same way over again. It should be correctable. Examples include an imporperly calibrated pH meter or a faulty buret
define random error or indeterminate error
arises from limitations in ability to make precise measurements and random fluctuations. It cannot be corrected Examples include reading scales and electrical nose in an insturment
define precision
a meausre of the reproducibility of your results
define accuracy
how close a measured value is to a true value
define absolute uncertainty
expresses the margin of uncertainty associated with a measurement e.g. 50 =/- 0.02 ml
define relativie uncertainty and give its equation
reltive uncertainty compares the absolute uncertainty with its asociated measurement. The equation is relative uncertainty= absolute uncertainty/ magnitude of measurement
Does systematic error effect accuracy or precision
Accuracy. The measurements will continue to be precise but they will be centered around the wrong value
Does random error effect accuracy or precision
precision. Random error is equaly likely to be positive or negative. It will cause your measurements to fall within a range of your true value
How is uncertaintly propagated when adding or substracting
The induvidual ABSOLUTE errors are squared and sumed. The sum of the squares is square rooted. This gives the absolute uncertaintly of the response
How is uncertainty propagated when multiplying and dividing
calcuate the relative percent errors, square then sum then take the square root. This gives the relative percent uncertainty of the answer
How do you convert relative % uncertainty to absolute error
divide by 100 to get back to the decimal then multiple by the magnitude of the measurement
how is error propagated in mixed operations
do addition and subtraction first and calcuate the absolute error. Then calcuate the % relative error and carry out multiplication like normal
What is the real rule of significant figures
the first uncertain figure of the answer is the last significant figure (the decimal places of the mesaurement and the absolute uncertainty should match)
what type of error does statistics deal with
random (indeterminate) error only
WHat aspects of a gaussian distribution to the mean and standard deviation determine
the mean determines the center and the standard deviation determines the width. The larger the standard deviation the more short and wide the curve
how do you calculate relative standard deviation
standard deviation divided by the average
what is variance
variance is the square of the standard deviation
What percentage of measurements lie within +/- 1 standard deviation from the mean of an ideal gaussian distribution
68.3%
What percentage of measurements lie within +/- 2 standard deviation from the mean of an ideal gaussian distribution
95.5%
What percentage of measurements lie within +/- 3 standard deviation from the mean of an ideal gaussian distribution
99.7%
what is a confidence interval
a range of values within which there is a specified probability of finding the true mean
How do you determine the degrees of freedom to use for calculating a confidence interval
The degrees of freedom is n-1 or number of data points -1
How do you find the T value for determining a confidence interval
find the degress of freedom an the % confidence desired then use the T table
T/F A 90% confidene interval is smaller than a 50% confidence interval
False, a 50% interval is smaller. To be 90% sure that we'll find the true mean, we have to have a large interval, if we are only 50% sure, we'll have a smaller value. Numerically, the t value for a 90% interval is larger than that for a 50% interval with the same DOF
what is the null hypothesis of the student's T test
the means are not different
how many degrees of freedom are used to find the T value when doing a comparison of means test
n1+n2-2
What does it mean it Tcalc> T table for a comparision of means test? What if Tcalc<T table
if Tcalc> T table, the two means are significantly different
If Tcalc<T table, the means are not different (note that we cannot say that the means are the same)
what is the fancy name for a known sample
Standard Refereance Material
How would calculate a confidence interval if you knew the population standard deviation
You would use the T value for infite degress of freedom
what equation would you use to compare your mean to a known value
T calc=(u-x) * (√n)/s)
How is a Grubbs test for an outlier preformed
Calculate the mean and standard deviation. Line the data up in order and look for a questionable values. Find G calc (questionable -average/ s) and compare to the table. If Gcalc> Gtable the questionable point should be discarded. Recalculate the new mean and standard deviation
What assumptions concerning vertical deviations are employed when using the least squares method for finding a best fit line (2)
1. The experimental uncertainties in the y values are greater than the uncertainties in the x values
2. The uncertainties for all of the y values are the same
describe the "ranges" of a calibration curve
1. linear range
2. dynamic range- data no longer shows a linear relationship but it can still be used
what is an R squared value
R squared describes how well a best fit line fits the data. The value ranges from 0-1 with 1 being a perfect fit
what are specifications
state how good measurements need to be and what procedural precautions will be used (sampling requirements, accuracy and precision, rates of false +/-, selectivity, sensitivity, accetable blank values, recovery of fortification, calibration checks, quality control)
define selectivity
being able to distinguish analyte from other species in the sample
define sensitivity
the capability of responding reliably and measurably to changes in analyte concentration
Define each type of blank
method-
reagent-
field-
method blank-sample containing all components except analyte
reagent blank-similar to a method blank but has not been subjected to all sample preparation procedures
field- similar to method blank but it has been exposed to the site of sampling
describe a spike recovery
a known quantity of analyte is added to a sample to test whether the response to a sample is the same as that expected from a calibration curve (example if a sample contains 10g and we add 5 g, we should expect to detect 15g)
How do you calculate spike recovery
%recovery= Cspiked-Cunspiked/ Cadded * 100
What is a calibration check
analyze solutions that contain a known amount of analyte and make sure they match the calibration curve
What are preformance test samples
blind samples that are used a a quality control method to eliminate bias introduced when an analyst knows then concentration
What is the detection limit
The smallest quantity of analyte that is "significantly different" from the blank
What is the difference between the detection limit and the lower limit of quantitation
the detection limit describes a point that is distinguishible from the blank but too small for accurate measurement. The lower limit of quantiation (10s/m)is the smallest amound that can be measured with resonable accuracy
What is the reporting limit
the concentration below which regulations dictate that a given analyte is reported as "not detected" Usually 5 to 10 times above the detection limit
What is the difference between signal detection limit and detection limit
signal detection limit is the limit of what is being analyzed e.g. absorbance. Dectection limit is the analyte that produced that signal e.g. concentration
what does the "s" stand for in the equations ydl=yblank + 3s, MDC= 3s/m, LOQ= 10s/m? What does the m stand for?
the S standands for the standard deviation of the y values (the measurements) the m is the slope of the calibration line
describe light waves
perpendicular oscillating electric and magnetic fields
what is wave number
the inverse of wavelength, usually expressed as cm-1
don't forget to inverse first before doing any conversions
what is the range of wavelengths and frequencies for x rays and what do they do to molecules
Frequency= 10^18
wavelength = 10^-11-10^-8
they cause bond breaking and ionization
what is the range of wavelengths and frequencies for UV rays and what do they do to molecules
Frequency =10^16
wavelenght 10^-8-10^-6
they cause electronic excitation
what is the range of wavelengths and frequencies for visable light and what do they do to molecules
Frequency 10^15
wavelength 400 (violet)- 700 (red) nm (10^-7)
many cause electronic exictiation but only near the violet end
what is the range of wavelengths and frequencies for infrared rays and what do they do to molecules
Frequency= 10^14-10^12
wavelength= 10^-6-10^-3
causes bond vibration and streching
what is the range of wavelengths and frequencies for microwaves and what do they do to molecules
Frequency= 10^9-10^8
wavelength= 10^-3 to 10^-1
causes bond rotation
Which end of the visible spectrum is most energetic
the violet end, 400nm (shorter wavelength, larger frequency, larger energy)
what is the equation for transmitance
T=P/Po
What are the components of a single beam spectrophotometer
1. light source
2. monochrometer
3. sample
4. light dectector
5. computer/ meter/ display
How do you convert from transmitance to absorbance
A=-logT (T is expressed as a decimal, not a percent)
What are the units of molar absorbtivity
M-1cm-1
What are the assumptions of beer's law
1. the light is monochromatic
2. the sample is dilute
what is the probabilty of a false positive using a +3s detection limit on a gaussian curve?
T distribution
0.15 % A false positive occcurs when a measurement that should fall within the blank distribution is mistaken for being within a measurement distribution. A 3s dection limit means that 99.7% of the measurements about the blank fall within the range of the blank. Half of the remaining measurements (0.3/2) = 0.15% are above this limit so they can be detected as positive when they are really not. The probablity of a false positive on a T distribution is about 1%.
What is the probability of detecting a false negative using a +3s dection limit on a guassian curve
There is a 50% probability of having a false negative. A false negative occurs when a measurement that should be within the sample distribution falls within the blank distrubution instead
Complement colors
red
orange
yellow
red & green
orange & blue
yellow & violet
Why is it necessary to use a flat peak portion of the absorbance spectrum when applying beer's law
If a flat region is chosen, small variations in wavelenth do not lead to signifiant changes in absorbance. If a steep region is chosen, small variations lead to large changes in absorbance (see graph)
the peak is used because it gives the greatest sensitivity
Why is it necessary to use dilute samples when applying beer's law
high concentrations decrese hte distance between particles leading to more interferace. They also decrease the light reaching the detector making the measurements less sensitive (if too little light gets through, intensity is hard to measure)
Why is it best to use a spectroeter at intermediate levels of absorbance (0.3 to 2)
too much light gets through- hard to distinguish from the blank
too little light- hard to measure intensity
What is the main benefit of a double beam spectrometer
it reduces the error assocaited with decetor or response drift that can occur between the reference and analyte measurements
Describe a double beam spectrometer
A light source is passed through a scanning monochrometer to select a narrow bandwidth. The light beam is then passed through a chopper which alternates the beam several times per second between the reference and sample cuvet. The beams are then send through a detector and the results are displayed
What types of light are usually used in spectroscopy and what sources are used to produce them
when do we swtch
1. visible light and infrared by tungesten filament (320-2500nm)
2. UV light with deuterium lamp (200 to 400)
switch is made at 360 nm from deuterium to tungsten
What is a monochrometer and how does it work
it breaks light into its component wavelenghts and selects the desired one
1. Radiation from the light source is made into parallel beams by a collimanating mirror
2.The parallel ways hit the grating and the different wavelenths are diffracted at different angles
3. The diffracted ligth hits a second mirror which focuses each wavelenth at a different point
4.A narrow band of wavelengths is detected towards the exit slit and allowed to pass through the sample
Rotation of the grating allows different wavelengths to pass throug the exit slit
What balance must be achieved with exit slit width
A narrow slit decreases the selected bandwidth which increases the resolution but decreases the energy reaching the detector which results in increased noise
describe a photomultipler tube spectrometer detector
light strikes a photosensitive cathode are electrons are emited these strike a seond surface called a dynode and more electrons are released. This process continues until about 10^6 electrons are released and collected for each photon striking the cathode. This translates very low light intesities into measurable electric signals
What is the disadvantage to the photomultipler tube dectetion method
only one wavelength can be measured at a time
Describe a photodiode array
White light passes through a sample. The beam then enters a polychromator which disperses the light into its wavelengths and directs it to the diode array.
What is the advantage to a photodiode array? Disadvantage?
advantage- detects entire sprectrum at once
disadvantage-about an order of magnitude lower resolution than a dispersive spec.
T/F the absorbance of a mixture is equal to the sum of the absorbances from all the species at that wavelenth
True
How can accuracy be improved when analysing the absorbance of a mixture
Pick wavelengths where one compound absorbs strongly and one asbors weakly,
what is an isobestic point
it is the point where two spectra of items in a mixture cross. For any mixture measure at the same wavelength with the same total cocentration, the IB point will be the same. It occurs when Ex=Ey (at the particular wavenlength) and [x] + [y] is constant
A=Esameb([x]+[y])
it is good evidence that only two principle species are present
what is the equation for corrected absorbance ina spectrophotometric titration
Abs cor= (total voume/ initial volume) (observed abs)
how is the end point detected in a spectrophotometric titration
we look for the point where the calibration line on the abs vs. volume added plot flatens
At the most basic level, what happens to a molecule that absorbs a photon? Emits a photon?
The molecule is promoted to a more energetic state
define singlet state
the electron spins are opposed (paired)
define triplet state
the electron spins are parallel (the same)
Which is lower energy S1 or T1
T1 has lower energy than S1
Draw the ground state
↑↓
----
Draw the S1 state

--

--
draw the T1 state

---

---
Assume a molecule absorbs a photon of sufficient energy to promote it from ground state So to S1. What is the usual next event
The molecule vibrationally relaxes to a lower level of S1, energy is lost to other molecule via collisions
describe an internal conversion
a molecule in S1 enters a highly excited vibrational level of So
describe an intersystem crossing
A molecule in S1 relaxes and then moves to an excited vibrational level of T1
How might a molecule relax from S1 back to ground state via emission of heat through collisions (2 ways)
1. S1 to R1 internal conversion to So R2 to ground state
2. S1 to R1 intersystem crossing to T1, R3, intersystem crossing to So, R4 to ground state So
What transition results in phosphorescence?
Flourescence?
Phosphorescence is T1 to So
Fluorsecence is S1 to So
What transition results in phosphorescence
T1 to So
T/F Phosphorescence and flurescenec can terminate in any vibrational level of So so long as it is not the ground state
True
Which occurs at lower energy Phosphorescence or fluroescence
Phosphorescence because it invovles a transition from T1 to So which is lower energy than S1 to So
Even though Phosphorescene occurs at lower energy than fluorescence it is rarer. Explain why
Phosphorescence requires a transition from T1 to So. Molecules in the T1 state are likely to undergo collisional deactivation before phosphorescence can occur
Describe the relationship between fluorescence and absorbance spectra
Fluorescence occurs at a lower energy than absorbance. It is roughly the mirror image of absorbance because the vibrational levels are roughly equal and the transition probabilites are similar
Besides electronic transitions what is another consquence of absorption of light
The breaking of chemical bonds (photochemistry), Also, some chemical reactions can release energy as light (chemoluminescence)
define luminescence
any emission of electromagnetic radiation. Includes fluorescence, phosphorescence, and other processes
How is luminescence measured
A sample is excited at a wavelength it absorbs and the wavelength of maximum emission is observed . The observation is made perpendicular to the incident direction to minimize the detection of scattered radiation.
Why is luminescence more sensitive than absorption
It is much easier to detect a light sample against a dark background than detecting a dark sample against a light backgroud (stadium candles example)
Describe a luminescence detector
A light source sends light to an excitation monochromater where one wavelength is selected. the light is sent through a sample cell where luminescence occurs at many wavelengths, These resultant wavelengths pass through another monochromater which selects for a dection wavelength. this wavelength is sent to the detector
What is the luminescence equation
I=kPoC
k is a constant
Po is the incident wavelenth
C is the concentration
and I is the intensity of luminescence
describe self absorption and how it effects the spectra
if the concentration of the analyte bceomes too great neighboring unexcited molecules absorb light from the excited molecule before the light can escape from the cuvet, this leads to an apparent decrease in fluorescence intensity at hight concentrations, the molecule quencehs its own emission
What to things must you do to a balance before you weight (besides making sure its clean and level)
calibrate and tare
how should a hygroscopic material be weight
You should weight by difference. Weigh a weight bottle, stoper and the material. Place it on the balance and tare. Remove some material from the bottle and place in into the reaction vessel. Note the difference as a negative value
What are some sources of determinate error when weight
evaporation of a liquid, fingerprints, weighing hot objects
What is the chemical name for THAM
tris-(hydroxylmethyl)aminomethane
What is THAM?
THAM is a primary standard weak base. It's structure consists of three HOCH2 groups connected to a central carbon which also has and NH2 group
Why is THAM a good primary standard base (6 reasons)
1. It is non-hygroscopic
2. it does not absorb carbon dioxide from the air
3. it is stable both as the solid and in aqueous solution
4. It can be prepared in very pure form
5. It can be dried without decomposition
6. It reacts quickly and stoichiometrically with the hydronium ion
What is the balanced chemical reaction for the THAM titration
THAM + HCL => (HOCH2)3CNH3+ + Cl-
why is it necessary to standardize an aproximate solution of NaOH
Analytical quality sodium hydroxie contains small amounts of impurites including water and carbonate.
What does KHP stand for
Potassium hydrogen phthalate
Why is KHP used for standardizing bases (4)
1. It is easily obtained in pure form
2. It has a high molecular weight
3. it is non hygroscopic
4. it is stable on drying
What is the balance reaction for the KHP titration
KHP +NaOH => KHC8H4O4 + H2O + Na+ (the Na plucks the acidic hydrogen from KHP giving water and the KHP anion
What is the acid base indicator used in the THAM + HCl titration and what is its color change? At what pH does this occur
bromocresol green
it is yellow as an acid and blue as a base it changes color a pH of 4.7 (intermediate green color)
What is the pH indicator used in the KHP + NaOH titration? What is it's color change and at what pH does this occur?
The indicator is phenophthalein. It is colorles when acidic and bright fusha when basic. The pH changes at about 9.2
How do you determine weight percent
mass of analyte/mass sample
what is the purpose of a positive control
-a calibration check used to check technique
-the answer is known in advance
-the goal is to prove that the data generated will be reliable
In what order were the reagents added to the iron reaction
1. HCL
2. NH2OH
3. NaOAc
4.Bipryidyl
what was the purpose of adding HCL to the iron mixture
it kept the pH low so that the iron complex would be stable
What was the purpose of adding NH2OH to the iron mixture
It is a reducing agent used to make sure all the iron is as Fe2+ (not Fe3+) which is the form that makes the complex
What was the purpose of adding NaOAc to the iron mixture
it is a buffer
What was the purpose of adding bipyridyl to the iron mixture
it is the reagent that forms the red complex with Fe2+
What is the advantage to using the precipitation from homogenous solution method for analysing Ca content
The precipitate forms slowly which gives larger crystals that are easier to handle. There are no zones of contact between relativley concentrated solutions
What is the purpose of the urea (NH2)2CO in the calcium oxalate precipitation
When urea is heated it begins a chain reaction of equations that evenually generate the oxalate ion needed to precipitate the Ca ions
Write the reactions that generate the calcium oxalate from urea + water + heat
(NH2)2CO + H20=> 2NH3 + CO2
2NH3 + H2C2O4=> 2NH4+ +C2O4 2-
Ca 2+ + C2O4 2- + H2O => CaC2O4. H2O (make sure to include the water in the molar mass)
How would you calculate % Ca of a sample from the final mass of calcium oxalate
Use the final mass of calcium oxalate and divide by the mass of the original sample. This gives a percent of CaCO4. Now change this percent into a decimal and multiply by the % Ca in CaCO4 (27.4296 g Ca/100 calcium oxalate)
What is the pupose of each of the following reactants in the calcium oxalate precipitation
urea
ammonium oxalate
urea + water and heat gives NH3, a weak base. THe NH3 reacts with the oxalic acid to release the oxalate anion. The Amonium oxalate supplies the oxalate anion and the HCl turns the oxalate anion into oxalic acid. This reactions allows for the slow generation of oxalate ions and controlled precipitation.