CHEM

26.1 MIDTERMS REVIEWER

Experiment 1: Application of Statistical Concepts in the
Determination of Weight Variation in Samples

Sample and Population
population collection of all measurements of interest
o parameter quantity that describes a
property of the population
sample refers to the subset of a population that is
representative of the population from which it was
collected
o statistic quantity that describes a property
of the sample; in the absence of determinate
errors, it is considered as a good estimate of
the parameter; reliability increases with the
number of measurements taken

Measures of Central Tendency
mean average of the values measured from the
sample; use a calculator to get this (x)

(x! + x! + x! + . . . x! )
x =

n

median middle value in a set of data that has been
arranged in increasing or decreasing order; if the set of
values is even, the median is the average of the 2
midpoints

Measures of Accuracy
absolute error, E difference between the
experimental value and true value

E = x! x!

relative error, Er absolute error divided by the true
value; expressed in percent

x! x !
E! =
x 100
x!

Measures of Precision
2
variance, s - measure of how far each value in the data
set is from the mean; use a calculator to get this (xn-
2
1); unit

!
!
!!! (x ! x)
s ! =

n 1

standard deviation, s square root of variance use a
calculator to get this (square of xn-1); same unit

s =

s
CV = x 100
x
pooled standard deviation, spooled used when there
are several data sets (n! ); same unit

s!""#$% =

!!
!!! (x !

x! )! +

!!
!!! (x !

x! )!

n! + n! + . .. n!
!

s! ! n! 1 + s! ! n! 1

n! + n! + . .. n!

range, R difference between highest and lowest

values in a set of measurements; same unit

!
!!! (x !

x)!

n 1

relative standard deviation, RSD - absolute value of the

coefficient of variation; unit is ppt
s
RSD = x 1000
x

Chem 26.1 Midterms Reviewer

coefficient of variation, CV RSD expressed in percent;

unit is %

R = x!"#!$%& x!"#$%&
relative range, RR range expressed in relative terms;
unit is ppt
R
RR = x 1000
x

Confidence Interval
provides a range of values within which the population
mean is expected to lie at a specified confidence level
uses n 1 in the table for values of t

ts
CI = x
n

Grubbs Test
used to detect outliers; can only detect 1 outlier per
data set
arrange data set from lowest to highest then calculate
|x! x| for both extremes, calculate gexp for the value
with a higher |x! x|
if gtab > gexp then the value is accepted, otherwise it is
rejected
o if gexp is rejected, calculate the new s and x for
the data set with the outlier removed
uses n in the table of critical values

max |x! x|
g = !!!..!

s

3 Types of Errors
gross errors
o outliers Grubbs test
o e.g.
arithmetic mistake
reading a scale backward
using a wrong scale
spilling a solution
systematic/determinate Errors
o have a definite value
o assignable cause
o affects accuracy
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1.

instrumental
faulty calibration
instrument
used
is
under
inappropriate condition
2. method
non-ideal chemical/physical behavior
of the chemicals
side reactions
impurities in the product
slight solubility of the
precipitate
incomplete reaction
minimize by:
blank determination
standard reference material
independent analysis
3. personal
prejudice in estimation
random/indeterminate
o affects precision
o sources: cannot be determined

Rate Law
A + B C + D
m
n
rate = k[A] [B]

where: k = rate constant


m & n = rate orders


m + n = overall reaction order

Graphical Method of Determining Rate Law

First

R = k[A]

Int. Rate
Law

[A]! = kt + [A]!

ln[A]! = kt + ln[A]!

Units of k

M

s

1

s

Linear Plot

[A]t vs. t

ln[A]t vs. t

Rate Law

Experiment 2: Solution Preparation and Standardization

Expressions of Concentration

moles solute
Molarity M =

L solution

moles solute
Molality m =

kg solvent

moles solute
Mole Fraction, X =

moles solution

Dilution

! ! = ! !

total volume of solution
Dilution Factor, DF =

volume of aliquot
M!"#!$#%&'%$( = M!"#$%&! x DF

volume of aliquot
1
Aliquot Factor, AF =
=
total volume of solution
DF
M!"#$%&! = M!"#!$#%&'%$( x AF


Experiment 3: Chemical Kinetics The Iodine Clock
Reaction

Chemical Kinetics
how fast or slow a reaction occurs

Factors
nature of reactants
concentration
temperature
presence of a catalyst
surface area

Chem 26.1 Midterms Reviewer

Zero

R = k

Slope
Half-life

-k

[A]!
=

2k

-k

ln (2)
=

k

Second

R = k[A]!


1
1
= kt +

[A]!
[A]!

1

Ms
!
[!]!

vs. t

k

1

k[A]!

Initial Rate Method

rate 1
k[A! ]! [B! ]!
=

rate 2
k[A ! ]! [B! ]!

Elementary Steps Method
include only the slow reaction and the steps before it
ex.

A + B C
fast

C + B D
slow

D E
fast
2


rate = k[A][B]

Arrhenius Equation

E! = Activation Energy
A = Arrhenius Constant

!!
!
ln k = ! + ln (A) [in the form y = mx + b]
!

where: R = 8.3124 & T is in Kelvin
!"#

linear regression on a calculator (Casio)
STAT A+BX enter x & y values
!
o x =

! (!"#$%&)

o y = ln (k)
press SHIFT + STAT go to Reg
o A = y intercept = b = ln A A = e!
!!
o B = slope = m = ! E! = mR
!

o
2

r ! = linearity = approaching 1
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Experiment

starch and iodine create a blue complex:
S! O! !! + 2I ! 2SO! !! + I!
persulfate + iodide sulfate + iodine

addition of thiosulfate creates a clock reaction:
2S! O! !! + I! S! O! !! + 2I !
thiosulfate + iodine tetrathionate + iodide

maintaining a constant ionic strength for all set-ups:
addition of KCl and K ! SO!

Experiment 4: Common Ion Effect and Buffers

Acid-Base Indicators
Indicator
pH values
Color

pH < 3.1
Red
Methyl Orange
3.1 < pH < 4.5
Salmon Pink
pH > 4.5
Yellow

pH < 8.3
Colorless
Phenolphthalein
8.3 < pH < 10.0
Very Light Pink
pH > 10.0
Red

Buffers
resists appreciable change in pH upon the addition of
small amounts of strong acid or strong base
composed of weak acid/base + conjugate ion
-
+
o HA & A or BH & B
buffer capacity amount of acid or base the buffer can
neutralize before pH begins to change to an
appreciable level
o = ! 1 or = ! 1

Determining the pH/pOH of Weak Acids/Bases
remember that:
o ! + !
o + ! ! + !
use ICE table to determine equilibrium concentrations
o when ! 10!! , x is negligible in addition
and subtraction operations
o change values if strong acid/base is added to
weak acid/base (addition of initial amount
present or calculation of limiting/excess
reactant when salt is formed)

[]
! ! =

[]

pK ! = log K ! & pK ! = log K !
K ! K ! = K ! = 1.00 x 10!!"

pH = log H ! & pOH = log [OH ! ]
14 = pH + pOH







Chem 26.1 Midterms Reviewer

Henderson-Hasselbalch Equation

pH = pK ! + log

[base]

[acid]

!!"# !"#$!!!"# !! !"".

addition of SA: pH = pK ! + log

!!"# !"#$!!!"# !! !"".

!!"# !"#$!!!"# !"! !"".

addition of SB: pH = pK ! + log

!!"# !"#$!!!"# !!! !"".

[acid]
pOH = pK ! + log

[base]

!!"# !"#$ !!!"# !"! !"".

addition of SB: pOH = pK ! + log

!!"# !"#$!!!"# !!! !"".

!!"# !"#$!!!"# !! !"".

addition of SA: pOH = pK ! + log

!!"# !"#$!!!"# !! !"".

Titration (For E5 & E6)

titrimetric analysis
quantitative
aims to determine concentration of analyte
uses a titrant of known concentration

requirements
fast
complete
known reaction
has a way to detect equivalence point

2 parts
standardization of titrant concentration using a
primary standard with
o high % purity
o high molecular weight
o high stability
o known reaction
sample analysis
o known titrant concentration and volume
o known analyte volume
o determine: analyte concentration

Experiment 5: Determination of the Solubility Product
Constant of Calcium Hydroxide

Solubility Product Constant

for a reaction: A ! B! xA!! + yB !!
(!)

K !" = [A!! ]! [B !! ]!

K !" is the product solubility constant
[A!! ]! [B !! ]! is the ion-product, IP, or reaction
quotient, Q, when the concentration used are initial
concentrations
solids do not appear as a denominator in the K !"
expression because the activity of any solid is 1
K !" is temperature dependent

When A!! ions were added to a solution with B !! ions:
3

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CO!

+ !

8.3

3.9

! ! + ! ! !

! + ! ()

Indicators
NaOH phenolphthalein
NaHCO! methyl orange
Na! CO! phenolphthalein + methyl orange

Relationship of
Substance
mmol of
VPH and VMO
Present
Substance
VMO = 0
NaOH
M!"# V!"
VPH = 0
NaHCO!
M!"# V!"
VPH = VMO
Na! CO!
M!"# V!"
M!"# V!"
VPH > VMO
Na! CO!
M!"# V!"
NaOH
M!"# (V!" V!" )
VPH < VMO
Na! CO!
M!"# V!"
NaHCO!
M!"# (V!" V!" )

Chem 26.1 Midterms Reviewer

Factors in the Experiment

use of boiled H! O
o removes CO! that can lead to carbonate error
(only present in sample with NaOH)
o CO! + 2OH ! CO! !! + H! O
instead of needing 2 moles H ! to
neutralize 2 moles OH ! , you only
need 1 mole H ! to neutralize 1 mole
CO! !!
carbonate error leads to a lower VPH
boiling near MO endpoint
o to obtain a sharper endpoint
o to disrupt ! ! + ! ! !



! + ! (!)
NaHCO! + NaOH Na! CO
+
! H! O
o impossible to determine original composition
o NaHCO! as the LR: Na! CO! + H! O + NaOH
o NaOH as the LR: Na! CO! + H! O + NaHCO!

Calculations

mg Na! CO!
%Na! CO! =
x 100
sample

mg NaHCO!
%NaHCO! =
x 100
sample

mg NaOH
%NaOH =
x 100
sample

%inert = 100 %Na! CO! %NaHCO! %NaOH

*use AF or DF as needed

Error Propagation

Addition and Subtraction
R = A + B C
r = a! + b ! + c !
final result: R r
o R follows the decimal place of r
o r should only have 1 significant figure

Multiplication and Division
R = AB C

resultant solution is unsaturated if IP < K !"

reaction mixture is saturated if IP = K !"
precipitation is observed if IP > K !"

Other Factors Affecting
common ion identical ion is added to solution
o lowers s - based on Le Chateliers principle,
the CI will shift the reaction backward
diverse-ion / ionic strength ion from a substance
containing no common ion is added to a solution
o increases with ionic strength (shielding)
1
=
! (! )!
2
where: C! = concentration of ion

Z! = charge of the ion

Calculations

Ca(OH)! ! Ca!! + 2OH !
K !" = Ca!! [OH ! ]!

[OH ! ] is calculated from HCl titration

Ca!! is OH ! / 2
compute using an ICE table
use 1:1 ratio for HCl standardization (only PH is used)

Experiment 6: Quantitative Determination of Soda Ash
Composition by Double Indicator Titration

Soda Ash Components
! ! - sodium carbonate
! - sodium bicarbonate
- sodium hydroxide

!!
!
!

! !

final result: R r
o R follows the decimal place of r
o r should only have 1 significant figure

! !

r=R

! !

Multiple Operations
ex. 1.5 0.1 + 2.6 0.2 / (1.4 0.3)
o addition: R = 4.1 and r = 0.2236067977

!.!

! !

!.!

division: r =

final result: 2.9 0.6

!.! !
!.!

/steffigatdula/