Experiment II
The Synthesis and Analysis of a Chromium
Salt
CHM120H5F
Teaching Assistant: Rima Rahmatullah
PRA9105
Date performed: 12-05-2021
Date submitted: 19-05-2021
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1. Introduction
K[Cr(C2O4)2(H2O)2]2H2O, chemically designated potassium dioxalatodiaquo
chromate(III)dihydrate, is a characteristic transition metal complex, which is formed
through the redox reaction of oxidizing potassium dichromate (K2Cr2O7) and reducing
oxalic acid dihydrate (H2C2O42H2O):
(1) K2Cr2O7(s) + 7H2C2O42H2O(aq) → 2K[Cr(C2O4)2(H2O)2]2H2O(aq) + 6CO2(g) + 13H2O(l)
Traditionally, metal complexes are constructed from a central metal atom engulfed by
molecules termed ligands. Accordingly, the chromium complex features a central
chromium atom, which is bound to four ligands: two of the bidentate oxalate and two
of the monodentate water varieties. These ligands are coordinated into specific
geometric isomer formations entitled cis and trans, in which the cis isomer features
two oxalate ligands on the same side of the chromium complex’s double bond whereas
the trans isomer showcases the oxalate ligands on opposite sides of the double bond.
Corresponding to their geometric difference, their natures tend to be divergent as the
trans isomer of the complex demonstrates higher stability and solubility in comparison
with its cis counterpart. Additionally, the chromium complex encompasses diverse
applications within the electrical industry, functioning as luminophores (molecules
instigating luminescent properties), solar cell dyes, and photoredox catalysts [2]. This
experiment will explore the synthesis of the cis isomer of the Cr +3 complex and the
analysis of the chromium metal content through the spectrophotometric calculation of
the Cr+3 cation concentration. Subsequently, the theoretical yield and Cr+3 ion
percentage will be quantified and evaluated against the actual yields and percentages
with the percent deviation being calculated, employing the equations:
(2) Sample of Chromium Complex (grams) × (1 mole of Chromium Complex
(mol)/Molecular Mass of Chromium Complex (grams)) = Theoretical #n mole (s)
of Chromium Complex (mol)
(3) Theoretical #n mole (s) of Limiting Reagent (mol) × (Molecular Mass of Product
(grams)/ 1 mole of Product (mol)]
(4) % yield deviation = ((actual – theoretical)/theoretical) × 100
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Lastly, the concentration of the chromium complex ion will be charted against the
absorbency in order to establish Beer-Lambert’s molar absorptivity, which is obtained
through the following equation:
(5) Absorbance = Molar Absorption Coefficient (M–1cm–1) × Molar Concentration (M)
× Optical Path Length (cm)
2. Experimental Methodology
Required Equipment:
- 2.0 grams of Potassium Dichromate
- 6.0 grams of Oxalic Acid
- 400 mL of boiling water in a 600 mL beaker
- Boiling chips
- Stirring hot plate
- Balance
- Evaporating dish
- Mortar and pestle
- 95% Ethanol
- Water
- Watch glass
- Glass rod
- Fume hood
- Funnel
- Spatula
- Sample vial
- Test tubes
- 100 mL beaker
- 0.5 grams of synthesized product
- 10% KOH
- Parafilm
- Test tube rack
- Centrifuge
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- Blank
- Hot water
- 16 molar Nitric Acid
- Spectrophotometer
- Cuvette
- Wipes
- 5 Chromium standard solutions
- Whatman 1 filter paper
All the required laboratory equipment was supplied by the Chemistry
department, and this experiment was performed in accordance with the procedure
detailed in the lab manual, referenced below [1], with no deviations except for the
addition of another set of absorbance values. The demonstrator begun the experiment
through the preparation of the steam bath, where 400 mL of distilled water was set to
boil and boiling chips were added to the beaker. Simultaneously, 2.0 g of potassium
chromate and 6.0 g of oxalic acid were grinded, followed by the weighing of the
evaporating dish. Subsequently, the grinded, powdered mixture was deposited in the
evaporating dish, stationed over the steam bath, and covered with a watch glass. Upon
completion, a purple-pigmented syrupy solution was generated and further stirred,
purified, and dissolved through the addition of 20 mL of 95% ethanol. Afterwards, the
remaining aqueous ethanol was decanted and the product was set aside in the fume
hood for 5 mins in order to cool. Once cooled, the evaporating dish retaining the
product (Cr+3 complex) was weighed out and the difference between the weight of the
evaporating dish and the evaporating dish + the product was utilized to derive the
weight of the product (4.2815 g). Successively, a majority of the chromium complex
was relocated to a sample vial in order to weigh out approximately 0.5 g for additional
analysis. 5 mL of distilled water and 5 mL of 10% KOH were added to the 0.5 g of
Cr+3 complex, followed by the mixing of the solution until a heterogenous mixture is
produced. The solution is then situated in the boiling water bath and left for 15 mins.
Once boiled, the solution’s test tube was removed from the water bath, washed with 4
mL of distilled water, and mixed well. Next, the solution was centrifuged at 3000 rpm
for 3 mins against three balance tubes (containing distilled water) with each centrifuge
followed by the decantation of most of the liquid in the solution, the addition of 10
mL of hot water, and the mixing of the solution. 2.5 mL of 16 molar nitric acid were
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added to the solution and then re-stationed within the boiling water bath for another
15 mins. Subsequently, a wavelength scan was conducted at λ 575 nm for an
unknown concentration of the Cr+3 complex and 5 standardized Cr+3 solutions. Once
the precipitate completely dissolved, the solution was filtered out, the test tube and
funnel were rinsed with distilled water, and the flask containing the Cr +3 solution was
washed with water until the mark on the flask was reached and mixed thoroughly.
Lastly, a wavelength scan was conducted for the prepared solution to measure the
solution’s absorbance.
3. Results
Figure 1 portrays the initial absorption spectra of the 0.050 M Cr(NO3)3(aq) from the
spectrophotometric analysis, which illustrates a maximum wavelength at approximately λ 575
nm.
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Table 1: The absorbance at λ 575 nm of Cr(NO3)3 for increasing concentration quantities
[Cr(NO3)3] 0.01 0.02 0.03 0.04 0.05
Absorbance
(O.D.) at 575
0.125 0.250 0.375 0.485 0.615
nm [Oct 26]
Absorbance
(O.D.) at 575
0.123 0.247 0.373 0.487 0.619
nm [Oct 29]
3.1. Observations
Potassium dichromate (K2Cr2O7) is a vibrant shade of orange with an apparent
crystalline structure whereas oxalic acid (H2C2O42H2O) is pure white with a similarly
noticeable crystalline structure. The heated, aqueous solution of K2Cr2O7 and
H2C2O42H2O resulted in a purplish-black syrupy solution with an adhesive and
glutinous appearance. The addition of more distilled water and the decantation of the
solution resulted in fragmented moist-looking sludge. However, when dried, the
precipitate from the solution appeared to obtain a coarse and powdery texture.
Furthermore, the solution returned to a purplish-black pigment upon the addition of
water, which transferred to a dark green pigmentation upon the addition of 10% KOH.
After the solution was heated in the boiling water bath, the green color lightened up a
few shades and became thicker in appearance (increase of precipitate present within
the solution). Following the three centrifuges, the precipitate possessed a dark green,
nearly black pigmentation while the green liquid became progressively lighter, nearly
transparent by the last centrifuge. Moreover, the addition of the nitric acid and the
subsequent heating transformed the color into a deep blue while the solution’s
pigmentation inside the concluding flask yielded a violet color. Lastly, as witnessed
through the 5 standardized Cr+3 complex solutions, the elevation of Cr+3 concentration
within the solutions yielded solution pigmentations that became progressively darker
and stronger.
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Cr(NO3)3 Calibration Curve
0.7
0.6 f(x) = 12.15 x + 0.00549999999999995
R² = 0.99947528774543
0.5
Absorbance at 575 nm
0.4
0.3
0.2
0.1
0
0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04 0.045 0.05 0.055
Concentration (M)
Calibration Curve 1 of Cr(NO3)3
Cr(NO3)3 Calibration Curve
0.7
0.6 f(x) = 12.15 x + 0.00549999999999995
R² = 0.99947528774543
0.5
Absorbance at 575 nm
0.4
0.3
0.2
0.1
0
0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04 0.045 0.05 0.055
Concentration (M)
Calibration Curve 2 of Cr(NO3)3
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3.2. Calculations
Theoretical Yield
Sample calculation:
K2Cr2O7:
1mol of K 2 Cr 2 O 7
2 g of K 2 Cr 2 O 7 × =6.80 ×10−3 mol K 2 Cr 2 O7 [Limiting Reagent]
294.185 of K 2 Cr 2 O7
H2C2O42H2O:
1 mol of H 2 C 2 O 4 2 H 2 O −3
6 g of H 2 C 2 O 4 2 H 2 O × =8.38× 10 mol H 2 C 2 O 4 2 H 2 O
716.0274 of H 2 C 2 O 4 2 H 2 O
−3
6.80 ×10 mol K ¿
Theoretical yield: 2.3065 g K[Cr(C2O4)2(H2O)2]2H2O
Percent Deviation between Theoretical and Actual Yields
Sample calculation:
4.2815 g K [Cr (C 2 O 4) 2( H 2O)2]2 H 2O
2.3065 g K ¿ ¿
Theoretical Percentage of Cr+3 in Product Synthesized
Sample calculation:
+3 52 g Cr+3
Percent of Cr =
339.1935 g K ¿ ¿
+3
Percent of Cr =15.33 %
Actual Percentage of Cr+3 in Product Synthesized
Sample calculation:
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0.527=12.15 x+0.0055
x=0.043 M
+3
Mole of Cr =0.043 M × 0.05 L
+3 −3 +3
Mole of Cr =2.15 ×10 mol Cr
52.00 gCr +3
Mass of Cr+3 =2.15× 10−3 mol Cr +3 ×
1 mol Cr +3
Mass of Cr+3 =0.1118 g Cr +3
0.1118 g Cr+ 3
+3
Percent of Cr =
0.527 g K ¿¿
+3
Percent of Cr =21.21%
Percent Deviation of Cr+3 Percentage between the Theoretical and Actual Yields
Sample calculation:
+3 |0.2121 g Cr +3−0.1533 g Cr +3|
Percent Deviation of Cr Percentage= ×100
0.1533 g Cr+3
+3
Percent Deviation of Cr Percentage=38.35 %
3.3. Reaction Equations
K2Cr2O7(s) + 7H2C2O42H2O(aq) → 2K[Cr(C2O4)2(H2O)2]2H2O(aq) + 6CO2(g) + 13H2O(l)
K[Cr(C2O4)2(H2O)2]2H2O(aq) + 3KOH → Cr(OH)3 + 4K+ + 2C2O4–2 + 4H2O
Cr(OH)3 + 3HNO3 → Cr(NO3)3 + 3H2O
4. Discussion
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The objective of this experiment was to explore the synthesis and analysis of
the cis isomer of the chromium complex K[Cr(C2O4)2(H2O)2]2H2O, quantify the
theoretical and experimental values of yields and chromium content within this
complex, and implement a comparative analysis between the theoretical and
experimental results. The theoretical and actual yields are 2.3065 g and 4.2815 g,
respectively, with a percentage deviation of 185%. The percentage deviation is
extremely large, which is indicative of either an error within the experimental study or
that the K[Cr(C2O4)2(H2O)2]2H2O yields fluctuate and are not centered around the
mean value. Additionally, the reasoning behind a larger experimental value in
comparison with its theoretical analogue could be due to the residual ethanol that had
not been decantated, residual liquid which failed to evaporate during the last test tube
heating, loss of other substances within the complex through numerous transfers,
and/or the improper measurements. The theoretical and actual percentages of
chromium content present within the K[Cr(C2O4)2(H2O)2]2H2O complex are 15.33%
and 21.21%, respectively, which correspond to a percent deviation of 38.35%. This
percent deviation, although not as extensive as the percent yield deviation, denotes
either an error has occurred within the experimental investigation and/or some of the
chromium content was lost through multiple transfers to different containers.
Similarly, this deviation could be resultant from an error, which occurred during the
spectrophotometry segment of the experiment. Insufficient wiping of the cuvette and
cracks and fragments present on the cuvette heavily impacts light absorbance and light
transmission.
Moreover, the oxidation-reduction reaction of oxidizing potassium dichromate
(K2Cr2O7) and reducing oxalic acid dihydrate (H 2C2O42H2O) with reactive KOH
generated a precipitated green solution, which reflects the extreme insolubility of the
product Cr(OH)3 and is suggestive of a low K sp quantity. The chromium derivative
insoluble characteristic aided and fostered its centrifuging and decanting capabilities.
On the other hand, the Cr(OH)3 molecules reaction with H(NO3)3 revealed the opposite
impact as H(NO3)3 exhibits a large Ksp quantity and completely dissolved the OH– ions,
causing the Cr+3 cations to accumulate within the aqueous media and is what allowed
for their spectrophotometric analysis.
5. Summary
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Conclusively, this laboratory report describes the synthesis of the chromium
salt K[Cr(C2O4)2(H2O)2]2H2O, the analysis incorporated between the complex’s
theoretical and experimental values of yields and chromium content within this
chromium complex, and the comparative analysis between the theoretical and
experimental results.
6. References
[1] Thottakad, R. Experiment 2 – Synthesis and Analysis of a Chromium Salt
(CHM110H5S), University of Toronto Mississauga, 2021
[2] Büldt, L. & Wenger, O. Chromium complexes for luminescence, solar
cells, photoredox catalysis, upconversion, and phototriggered NO release, Chem.
Sci., 2017
7. Learning Objectives
- Understanding the methodology behind synthesizing transition metal complexes
- Attaining better understanding, awareness, and recognition of laboratory
equipment and procedures
- Understanding and familiarizing yourself with the centrifuging and the way to
safely and correctly operate this procedure
- Gaining insight into concepts learned in class and their various applications
8. Appendix
Data Sheet
Data Sheet
Name: Malak Mahmoud Student No.: 1006825170
Lab Section No.: PRA9109 Date: 10-02-2021
1. Calibration Curve
Attach your absorption spectrum to this data sheet.
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[Cr(NO3)3] 0.01 0.02 0.03 0.04 0.05
Absorbance
(O.D.) at 575
0.125 0.250 0.375 0.485 0.615
nm [Oct 26]
Absorbance
(O.D.) at 575
0.123 0.247 0.373 0.487 0.619
nm [Oct 29]
2. Synthesis
Weight of Evaporating Dish: 104.0992 grams
Weight of Evaporating Dish + Product: 108.3807 grams
Weight of Product: 4.2815 grams
3. Analysis
Weight of Sample: 0.5012 grams
Absorbance (O.D.) of Solution at 575 nm: 0.615
Absorbance (O.D.) of Prepared Solution at 575 nm: 0.527
4. Observations
- Purple, syrup-like solution as the product
- The product is washed with ethanol to further dissolve the organic compounds in the
product, to reduce any contamination, and to purify our product.
- In order to calculate the theoretical yield, the mass of the reactants are given in grams
are used with the molecular masses to obtain the moles, which are utilized to
determine the limiting reagent.
- The reaction between the chromium complex and KOH yields a green precipitate
(Cr(OH)3)
- A centrifuge is used to separate the precipitate from the liquid, which will be spinning
at 3000 rpm for 3 minutes. The liquid is a lighter green color in comparison to the
dark green color of the precipitate.
- The second round of centrifuging resulted in a much lighter, almost transparent green
liquid with a much darker, almost greenish-black precipitate.
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- The third round of centrifuging with hot water resulted in a colorless liquid with a
greenish-black precipitate.
- The cuvette is wiped down and checked for scratches or bubbles, which is crucial as
these factors can intercept the pathway of light and affect absorbance measurements.
Academic Integrity Checklist
Report Name: Experiment II – The Synthesis and Analysis of a Chromium Salt
Course Name: CHM120H5F
TA’s Name: Rima Rahmatullah
I, Malak Mahmoud, affirm that this assignment represents entirely my own efforts. I
confirm that:
- I have acknowledged the use of another’s ideas with accurate citations.
- If I used the words of another (e.g., author, instructor, information source), I have
acknowledged this with quotation marks and proper citation.
- When paraphrasing the work of others, I used my own words (not merely using
synonyms or rearranging the sentence structure). I have also appropriately cited the
source(s) of the idea(s).
- I have checked my work against my notes to be sure I have correctly referenced all
direct quotes or borrowed ideas.
- My bibliography includes only the sources used to complete this assignment.
- This is the first time I have submitted this assignment (in whole or in part) for
academic credit in any year and/or at any institution.
- Any proofreading by another was limited to indicating areas of concern which I then
corrected myself. All changes (including grammar correction) were entirely my own.
- This is the final version of my assignment and not a draft. I have kept and will
continue to keep my work to myself and did not/will not share answers or content
with others, unless otherwise directed by my instructor.
- I understand the consequences of violating the University of Toronto’ academic
integrity policies as outlined in the Code of Behaviour on Academic Matters.
By signing this form, I agree that the statements above are true. If I do not agree with the
statements above, I will not submit my assignment and will consult the course instructor
immediately.
Student name: Malak Mahmoud
Signature: M.M.
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Date: 19-05-2021
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