Review of Fundamental Concepts

(Gary Christian, hal 65)

Atomic, and Molecular Weights
Atomic weight (BA)for any elements is the weight of a specified
number of atoms of that element, and that number is the same
from one to another.
Examples: Ca 40.08, S 32.06, O 16.00
Molecular weight (BM) is the sum of formula weight of the
atoms that make up compound.
Example: Calculate the number of grams in one mole of
CaSO
4
.7H
2
O
= Ca + S + 11xO + 14xH
= 40.08+32.06+11x16.00+14x1.09
= 262.25

Moles, Molarity, Normality
Mole = grams/formula weight

Molarity = mole/liter
1 mol dalam 1 liter larutan

Example: A solution is prepared by dissolving 1,26 g
AgNO
3
in a 250 ml volumetric flask and diluting to
volume. Calculate the molarity of the silver nitrate
solution. How many millimoles AgNO
3
were
dissolved?
Moles, Molarity, Normality
Answer




Millimoles
millimole = M x milliliter
= 0.0297x250
= 7.42 mmole

Persen berat/berat
% (wt/wt)
= (berat zat terlarut) x 100%
(berat sampel)
= (g zat terlarut/g sampel) x 100 %

Common Units for Expressing Trace
Calculations
Parts per million (ppm)

= (berat terlarut/berat sampel) x 10
6

= mg/kg = mg/L = L/L
= g/g = g/mL = nL/mL
Example.
A 2.6 g sample of plant tissue was analyzed and found to contain 3.6 g zinc.
What is the concentration of zinc in the plant in ppm

Answer :
berat zat 3,6 ug
berat sampel 2,6 gram
konsentrasi zinc dlm sampel = 3.6 g/2.6 g atau
= (3.6 x 10
-6
/2.6) x 10
6

= 1.4 ppm
Satuan lainnya....
ppt (part per thousand)

= (berat zat terlarut (g)/berat
sampel (g)) x 10
3


= mg/g

= g/kg


ppb (part per billion)

= (berat zat terlarut/berat sampel)
x 10
9


= ng/g

= ug/kg

Contoh soal
Berapa mg sampel yang harus ditimbang jika ingin membuat 50 ppm
dalam 100 ml.

50 ppm = (x gram/100 ml) x 10
6

x = 50 x 100
10
6
=
5 x 10
-3
gram
=
5 mg

Atau ppm = ug/ml
50 ppm = ..... g/100 ml
50 ppm x 100 ml = 5000 g
= 5 mg
Contoh soal
Hitung berapa Molar jika BM = 100 dengan
konsentrasi 1 ppm

ppm = mg/L = 10
-3
gram/L
M = gram/BM/L
M = 10
-3
/100/L
= 10
-5
mol/L
= 10
-5
M
Soal
Hitung :
a. 1 ppm berapa persen?
b. 1 ppb berapa persen? Dan berapa ppm?
Jawab :
1 ppm = 10
-4
%
1 ppb = 10
-7 %
= 10
-3
ppm
General calculation with
Molarity
Consider the general reaction

a A + t T P

Where A is the analyte, T is the titrant, reacting in the ratio a/t to give products P, then

mmol
A
= mmol
T
x a
t
mmol
A
= M
T
x ml
T
x a
t
mg
A
= mmol
T
x BM
A
x a
t
mgA

= M
T
x ml
T
x a x BM
A

t



Fraction..
% A = Fraction analyte x 100 %
= mg
analyte x
100 %

mg
sample
=
mmol
titrant
x (a/t) x BM x 100 %
mg sample
= M
t
x ml
t
x

a/t x BM x 100 %
mg sample
Example
A 0,2638 gram soda ash sample is analyzed by titrating the
sodium carbonate with the standard 0,1288 M hydrochloric
solution, requiring 38, 27 ml.
The reaction is
CO
3
2-
+ 2H
+
---- H
2
CO
3
+ CO


milimoles of sodium carbonate is equal to one-half the
milimoles of acid used to titrate it, since they react in a 1:2
ratio (a/t = )

% = M
T
x ml
T
x a/t x BM
A
x 100%
mg sample
Normality
Many substance do not react on a 1:1 mole basis.
And so solution of equal molar concentration do not react on a 1:1 volume
basis.
-----consepts of equivalents and normality (N)

N = number of equivalents of material per liter solution

N = eq = meq
L mL
(eq) = Number of equivalent

eq = mol x no. Of reacting units per molecule
Normalitas
Banyaknya ekivalen (ek) zat terlarut tiap liter
larutan, atau
N = ek/V

ek = gram/BE BE = BM/n

N = (gram x n) / (BM x V)


Berat Ekivalen (BE)
BE = berat molekul dibagi dengan valensi
= BM/n
Cara penentuan valensi bergantung pada reaksi yang
terjadi
Cara penentuan valensi
a. Reaksi asam basa, valensi ditentukan berdasarkan
banyaknya H
+
atau OH
-
yang dihasilkan tiap satu
mol asam atau basa
b. Reaksi redoks, valensinya ditentukan o/ banyaknya
elektron yang hilang atau timbul pada reaksi
oksidasi reduksi
Contoh :

a. H
3
PO
4
: 1 mol ekivalen dengan 3 mol ion H
+
b. Ca(OH)
2
: valensinya 2
c. I
2
+ 2e ----- 2I
-

maka valensinya = 2 sebab 1 mol ekivalen dengan 2
elektron
Contoh soal
Hitung berat ekivalen Na
2
C
2
O
4
dan KMnO
4
dlm reaksi
redoks suasana asam
The Equivalent Weight
Berat ekivalen sama dengan berat molekul dibagi dengan valensi

For example :
HCl, eq. Wt (BE) = the formula weight

H
2
SO
4
it takes only one-half the number of molecules to furnish one mole of H
+
,
so eq.wt = one half the formula weight

eq.wt H
2
SO
4
= f.wt
2

eq = gram
eq. Wt (BE)

N = eq = gram/BE
L L

T
Example: Calculate the equivalent weights f the following substances: (a) NH
3
(b) H
2
C
2
O
4
(c) KMnO
4
(MnO
4
-
is reduced to Mn
2+
)
Solution
(a) eq. wt. = NH
3
/1 =17.03/1
(b) Eq. wt. = 90.04/2 = 45.02
(c) The Mn goes a five electron change, from valence +7
to +2:
MnO
4
-
+ 8 H
+
+ 5e
-
= Mn
2+ +
4H
2
O
Eq. wt. = 158.04/5 = 31.608
Example: Calculate the normality of the solutions containing the
following (a) 5.30 g/L Na
2
CO
3
(b) 5.267 g/L K
2
Cr
2
O
7

Solution
(a) CO
3
2-
reacts with 2H
+
to H
2
CO
3

N=5,3/105.99/2 =0.1000 eq/L
(a) Each Cr
4+
is reduced to Cr
3+
, a total change of 6e
-
/molecule K
2
Cr
2
O
7

Cr
2
O
7
2-
+ 14H
+
+ 6e
-
= 2Cr
3+
+ 7H
2
O
N=5,267/294.19/6 =0.1074 eq/L

Keuntungan menggunakan satuan
Normalitas
The advantage of expressing concentrations in
normality and quantities as equivalents is that one
equivalent of substance A will ALWAYS react with
one equivalent of substance B.

NaOH (= 1mol) will react with one equivalent of
HCl (=1 mol), or with one equivalent of H
2
SO
4
(1/2
mol)

Cont`n....
We can, calculate the weight of analyte from the
number of equivalents of titrant, because the latter
is equal to equivalents of analyte.

meq
A
= meq
T
meq
A
= mg
A
= N
T
x mL
BE
A
mg
A
= N
T
x mL
T
x BE
A

How about the equation for calculating the percent of
a constituent in the sample????

Example
A 0,467 g sample containing sodium bicarbonate (a
monoacidic base) and titrated with a standard solution of
HCl, requairing 40,72 ml. The hydrocloric acid was
standarized by titrating 0,1876 g sodium carbonate, wich
required 37,86 ml. Calculate the percent sodium bicarbonate
in the sample.
Solution :
N
HCl
= meq Na2CO
3 =
mg/BE (BM)

mL HCl mL

Persen NaHCO
3
= ....................


Density (kerapatan) calculation
Density is required for a calculation of molarity
Density is the weight per unit volume at the specified
temperature, usually g/mL at 20C.

= gram/mL

Example: How many millimiters of concentrated sulfuric acid
94% (g/100g solution) density 1.843 g/cm
3
are required to
prepare 1 L of 0,100M solution?


Penyelesaian
Consider 1 cm
3
= 1 mL.
From density For 1 L solution = 1843 g solution
From percent g H
2
SO
4
= 94% x 1843 = 1732.42
Mole H
2
SO
4
= g/BM = 1732.42/98 = 17.68 mol in 1 L
solution
M= 17.68
Mole Initial = Mol Final
17.68 x V H
2
SO
4
= 0.1 x 1000 V = 5.66 mL

Gram is basic unit of massa and is the unit
employed most often in macro analyses
For small sample, smaller unit are employed
mg = 10
-3
gram
ug = 10
-6
gram
ng = 10
-9
gram
pico = 10
-12
gram
femto = 10-
15
gram
Problems
Calculate the molar concentration of all the cations and anions in a
solution prepared by mixing 10.0 mL each of the following solutions:
0.100 M Mn(NO
3
)
2
, 0.100 M KNO
3
, 0.100 M K
2
SO
4
.
Calculate the grams of each substance required to prepare the
following solution: (a) 250 mL of 0.100 M KOH (b) 1.00L of 0.0275 M
K
2
Cr
2
O
7
(c) 500 mL of 0.500 M CuSO
4

How many milliliters of concentrated hydrochloric acid, 38% (wt/wt),
specific gravity 1.19, are required to prepare 1L of a 0.100 M solution
You have a 250 ppm solution of K
+
as KCl. You wish to prepare from this
a 0.00100 M solution of Cl
-
. How many milliliters must be diluted to 1
L?

Solution
Problems
How many milliliters of 0.10 M of H
2
SO
4
must be added to 50 mL of 0.1 M
NaOH to give a solution that is 0.050 M in H
2
SO
4
? Assumes volumes are
additive.
A 0.500 g sample is analyzed spectrophotometrically for manganese by
dissolving it in acid and transferring to 250 mL flask and diluting to volume.
Three aliquots are analyzed by transferring 50 mL portions with a pipet to 500
mL Erlenmeyer flasks and reacting with an oxidizing agent, potassium
peroxydisulfate, to convert the manganese to permanganate. After reaction,
these are quantitatively transferred to 250 mL volumetric flasks, diluted to
volume, and measured spectrometrically. By comparison with standards, the
average concentration in the final solution is determined to be 1.25 x 10
-5
M.
What is the percent manganese in the sample?
Solution
Problems
A preparation of soda ash is known to contain 98.6% Na
2
CO
3
. If a 0.678
g sample requires 36.8 ml of sulfuric acid to complete neutralization,
what is the molarity of the sulfuric acid solution?
A sample of USP grade citric acid (H
3
C
6
O
7
, three titratable protons) is
analyzed by titrating with 0.1087 M NaOH. If a 0.2678 g sample
requires 38.31 ml for titration, what is the purity of the preparation?
(USP requires 99.5%)

Solution
Problems
A solution is prepared by dissolving 7.82 g NaOH and 9.26 g Ba(OH)
2
in water
and diluting to 500 ml. What is the normality of the solution as a base?
What weight of arsenic trioxide, As
2
O
3
, is required to prepare 1L of 0.1000 N
arsenic (III) solution?
The sulfur content of steel sample is determined by converting it to H
2
S gas,
absorbing the H
2
S in 10 ml of 0.00500 M I
2
, and then back titrating the excess
I
2
with 0.00200M Na
2
S
2
O
3
. If 2.6 ml Na
2
S
2
O
3
is required for titration, how
many milligrams of sulfur are contained in the sample?
A potassium permanganate solution is prepared by dissolving 4.68 g KMnO
4
in
water and diluting to 500 ml. How many milliliters of this will react with the
iron in 0.500 g of ore containing 35.6% Fe
2
O
3
?

Solution