An Experiment Safety Plan(ESP) is required for every experiment conducted within the Department, including those experiments performed by Department Employees/Students at a location away from Jett Hall. The purpose of the ESP is to assure the safety of all by identifying the safest possible methods to conduct an experiment. By signing below the individual(s) conducting the experiment, Chemical Hygiene Officer (CHO), and the faculty advisor acknowledge responsibility forthe following requirements.

1)Appropriate Personal Protective Equipment (PPE) mustalways be worn while in the lab(as described in the ESP). The minimum required PPE to entera research/teaching lab in Jett Hall is (1) long pants, (2) closed toe shoes, (3) lab coat or long sleeve shirt, and (4) safety glasses with side shields.

2)For safety reasons, no researcher is permitted to work alone in the lab at any time. Because the labsare open 24/7, there may be occasions (such as a late night or over weekends) when there are no other people working in the lab. If you plan to work during a time when the lab might be expected to be empty, please plan ahead and coordinate your work schedule with another lab member.

3)Trainingmust becompletedprior to working the experiment in the lab. The minimum required training to enter the lab can be completedthrough EH&S and includes the following courses:
(1) Employee & HAZCOM Safety, (2) Lab Standard, (3) Hazardous Waste Management and (4) the SACHE certification "Basics of Laboratory Safety." Researchers must attend the annuallab refresher seminar. Other training may be required by the CHO or EH&S personnel based on the ESP review.

4)ESP approval occurs in two phases. Phase I is the preparation of a written safety plan. Uponapproval of the written plan, researcher(s) may order equipment and necessary supplies, and begin to assemble experiment. Phase I also includes an evaluation by CHO (and if appropriate by EH&S) to establish controls of hazardous operations, avoid the purchase of inappropriate supplies, and establish expected waste(s) streams. Phase IIapproval requires evaluationof the assembled experiment, and a “dry run” of the experimental procedure or Emergency Shutdown Procedure.High Hazard work may be subject to approval by official university boards, including any work with radioactive materials or radiation producing machines, certain biological materials, animals and/or human subjects.

Date
ESP Phase I approval:
Department Head
ESP Phase II approval
Chemical Hygiene Officer

5)By signing below, both faculty advisor and researchers(s) understand that the CHO can approve/disapprove any part of the ESP. The CHO can further assemble a committee of individuals with appropriate technical or EH&S background to assist in reviewing the ESP. It is the goal of the CHO to help the researcher(s) find the safest method(s) of conducting an experiment. The CHO, or any faculty member, may stop lab activity of individuals not following good lab practices.

Name / Signature / Date
Faculty Advisor
Researcher
Researcher
COE Safety
EH&S (at requestof CHO)

1

Name/Title of Experiment: / Briggs-Rauscher Reaction
Building and Room Number:
Location within Room: / Fume Hood / Tabletop in an undefined location (such as in a school gymnasium).
Emergency Contacts: / EMERGENCY / 911
Department Engineer / Meng Zhou / (575) 646-1214
Faculty Advisor
Department Head / David Rockstraw / (575) 635-9539
Responsible Researcher

Required attachments to the ESP:

Attachment 1:Experiment Scope

Attachment 2:Drawing of the laboratory or pilot area

Attachment 3:Normal Operations, Startup and Shutdown Procedures

Attachment 4:Emergency Shutdown Procedure and medical emergency instructions.

Attachment 5:Waste Management Procedure

Attachment 6:Hazard Identification and Mitigation

Attachment 7:Material Safety Data Sheets

1

Provide a concise description of the laboratory experiment to be undertaken.

  1. Explain why the work is being performed, the goal(s) of the experimental program
  2. Provide the stoichiometry of any chemical reactions and theirheats of reaction
  3. Demonstrate the inherent thermal safety of your experiment through calculation or through the use of accelerating rate calorimetry data.
    (
  4. Include a complete list of all chemicals (reactants and products) involved in the work.
  5. Include a complete list of all equipment (e.g. autoclave, centrifuge, pump, heat bath etc.) involved in this work

This experiment is to demonstrate a chemical engineers skills to students in grades school and middle school.

Goals of this experiment:

  • To demonstrate chemistry to school age children
  • To encourage students to pursue chemical engineering as a degree course

Taken from: Oscillating reaction - Briggs-Rauscher reaction. University of Leeds:

“In the BR reaction the evolution of oxygen and carbon dioxide gases and the concentrations of iodine and iodide ions oscillate. The somewhat simplified mechanism of this reaction can be represented by the following overall transformation:

IO3-+ 2 H2O2+ CH2(COOH)2+ H+==> ICH(COOH)2+ 2 O2+ 3 H2O (11.1)

This transformation is accomplished through two component reactions:

IO3-+ 2 H2O2+ H+==> HIO + 2 O2+ 2 H2O (11.2)

HIO + CH2(COOH)2==> ICH(COOH)2+ H2O (11.3)

The first of these two reactions can occurviatwo different processes, a radical process and a nonradical process. Which of these two processes dominates is determined by the concentration of iodide ions in the solution. When [I-] is low, the radical process dominates; when [I-] is high, the nonradical process is the dominant one. The second reaction (eq. (11.3)) couples the two processes. The reaction consumes HIO more slowly than that species is produced by the radical process when that process is dominant, but it consumes HIO more rapidly than it is produced by the nonradical process. Any HIO which does not react by eq. (11.3) is reduced to I-by hydrogen peroxide as one of the component steps of the nonradical process for reaction (11.2). When HIO is produced rapidly by the radical process, the excess forms the iodide ions, which shut off that radical process and start the slower nonradical process. Reaction (11.3) then consumes the HIO so rapidly that not enough is available to produce the iodide ion necessary to keep the nonradical process going, and the radical process starts again. Each of the processes of reaction (11.2) produces conditions favorable to the other process, and, therefore, the reaction oscillates between these two processes.

The detailed explanation requires attention to the individual steps of the two processes. If iodide ions are present in sufficient concentration, the reaction follows the nonradical process, reaction (11.2). The iodide ions react rather slowly with iodate ions,

IO3-+ I-+ 2 H+==> HIO2+ HIO (11.4)

The iodous acid (HIO2) is further reduced to hypoiodous acid (HIO),

HIO2+ I-+ H+==> 2 HIO (11.5)

The hypoiodous acid is then reduced by hydrogen peroxide,

HIO + H2O2==> I-+ O2+ H++ H2O (11.6)

The net transformation represented by eq. (11.2) is obtained by the stoichiometric addition of eq. (11.4) + eq. (11.5) + eq. (11.6).

Because reaction (11.2) is slower than reaction (11.3) under these conditions, so much HIO is used up by reaction (11.3) that reaction (11.6) cannot replenish the I-consumed in reactions (11.4) and (11.5); the [I-] keeps diminishing.

Once the iodide ions have been sufficiently depleted, the nonradical process becomes very slow, and the radical process for reaction (11.2) can take over. This process involves the five steps [3].

IO3-+ HIO2+ H+==> 2 IO2·+ H2O (11.7)

IO2·+ Mn2++ H2O ==> HIO2+ Mn(OH)2+ (11.8)

Mn2++ H2O2==> Mn2++ H2O + HOO· (11.9)

2 HOO·==> H2O2+ O2 (11.10)

2 HIO2==>IO3-+ HIO + H+(11.11)

These steps, when combined in the stoichiometry of 2 (eq. (11.7)) + 4 (eq. (11.8)) + 4 (eq. (11.9)) + 2 (eq. (11.10)) + eq. (11.11), have the overall result given by eq. (11.2). A significant feature of this process is that, taken together, the first two steps (eqs. (11.7) and (11.8)) are autocatalytic - they produce 2 HIO2for each one consumed. Therefore, the rate of these steps increases as they occur. Because this radical process is autocatalytic, it causes a rapid increase in the concentration of HIO, which is produced by the disproportionation of HIO2(eq. (11.11)). This process does not rapidly consume all the iodate in the solution, because the last step is second order in the catalytic species. Thus, as its concentration increases because of the autocatalytic nature of the early steps, HIO2is ever more rapidly consumed in this last step, and the sequence of the reactions quickly reaches a steady state.

Equations (11.8) and (11.9) indicate the function of the manganese catalyst. The manganese is oxidized in reaction (11.8) and reduced in reaction (11.9). Its catalytic effect in the reaction is accounted for through its providing the means for reducing IO2·radicals to HIO2, thereby completing the autocatalytic cycle of equations (11.7) and (11.8).

The hypoiodous acid produced by the radical process reacts with malonic acid by reaction (11.3). However, the radical process is faster than reaction (11.3), and the excess HIO reacts with hydrogen peroxide by reaction (11.6) to create I-, which shuts off the radical process and returns the system to the slow nonradical process initiated by reaction (11.4).

The dramatic color effects arise because reaction (11.3) does not take place in a single step, but by the sequence of reactions (11.12) and (11.13).

I-+ HIO + H+==> I2+ H2O (11.12)

I2+ CH2(COOH)2==> ICH(COOH)2+ H++ I- (11.13)

The solution turns amber from the I2produced through reaction (11.12), when the radical process maintains [HIO] greater than [I-]. The excess HIO is converted to I-through the reaction with H2O2(eq. (11.6)). The solution suddenly turns dark blue when [I-] becomes greater than [HIO], and the I-can combine with I2to form a complex with the starch. With [I-] high, reaction (11.2) switches to the slow nonradical process. The color then fades as reaction (11.3) consumes iodine faster than it is produced. When the system switches back to the rapid radical process, the cycle is repeated.

The above reaction steps constitute a skeleton mechanism for the BR oscillating reaction. Upon initial mixing of the solutions, IO3-reacts with H2O2to produce a little HIO2. The HIO2reacts with IO3-in the first step of the radical process (eq. 11.7). The autocatalytic radical process follows, rapidly increasing the concentration of HIO. The HIO is reduced to I-in a reaction with H2O2(eq. 11.6). The large amount of HIO reacts with I-, producing I2(eq. 11.12). The I2reacts slowly with malonic acid, but the concentration of HIO, I2and I-all increase, because reaction (11.2) is faster than reaction (11.3). As [I-] increases, the rate of its reaction with HIO2(eq. 11.5) surpasses that of the autocatalytic sequence of reactions (11.7) and (11.8). The radical process is then shut off, and the accumulation of reduced iodine is consumed by reaction (11.3) operating through the sequence of reactions (11.12) and (11.13). Eventually [I-] is reduced to such a low value that reactions (11.7) and (11.8) become faster than reaction (11.5), and the radical process takes over again. This oscillating sequence repeats until the malonic acid or IO3-is depleted.

Chloride ion concentrations in excess of 0.07 M suppress the oscillations. Therefore the vessels used for the preparation of the solutions must be clean and distilled water must be used for all preparations.”

References:

School of Chemistry. (2010, 5 12). Oscillating reaction - Briggs-Rauscher reaction. Retrieved from University of Leeds:

IO3-+ 2 H2O2+ CH2(COOH)2+ H+==> ICH(COOH)2+ 2 O2+ 3 H2O(11.1)

IO3-+ 2 H2O2+ H+==> HIO + 2 O2+ 2 H2O(11.2) ΔHrxn = 166.7 kJ/mol

HIO + CH2(COOH)2==> ICH(COOH)2+ H2O (11.3)ΔHrxn = ? kJ/mol

IO3-+ I-+ 2 H+==> HIO2+ HIO (11.4)ΔHrxn = 553.6 kJ/mol

HIO2+ I-+ H+==> 2 HIO (11.5)ΔHrxn = 186.6 kJ/mol

HIO + H2O2==> I-+ O2+ H++ H2O (11.6)ΔHrxn = -286.8 kJ/mol

IO3-+ HIO2+ H+==> 2 IO2·+ H2O (11.7)ΔHrxn = -305.7 kJ/mol

IO2·+ Mn2++ H2O ==> HIO2+ Mn(OH)2+ (11.8)ΔHrxn = 249.7 kJ/mol

Mn2++ H2O2==> Mn2++ H2O + HOO· (11.9)ΔHrxn = -84.7 kJ/mol

2 HOO·==> H2O2+ O2 (11.10)ΔHrxn = -214.6 kJ/mol

2 HIO2==>IO3-+ HIO + H+ (11.11)ΔHrxn = -367.0 kJ/mol

I-+ HIO + H+==> I2+ H2O (11.12)ΔHrxn = -363.7 kJ/mol

I2+ CH2(COOH)2==> ICH(COOH)2+ H++ I- (11.13)ΔHrxn = ? kJ/mol

Kill Reaction:

I2 + 2 S2O32-==> S4O62- + 2 I- (Iodine Clock Reaction)ΔHrxn = ? kJ/mol

Chemicals to be used:

  • 4.3 g potassium iodate (KIO3)
  • 10 mL 1 M sulfuric acid (H2SO4)
  • Deionized water
  • 1.5 g malonic acid (HOOCCH2COOH)
  • 0.4 g manganese sulfate monohydrate (MnSO4. H2O)
  • 30 mL of 30% hydrogen peroxide (H2O2)
  • 0.1 g of soluble starch
  • ~4 g sodium thiosulfate (Na2S2O3)

Chemicals produced:

  • ICH(CO2H)2
  • Oxygen (O2)
  • Water (H2O)

Equipment to be used:

  • 3 100mL beakers
  • Tongs
  • 3 Graduated cylinders
  • Heated stirring plate
  • Magnetic stir bar
  • Three 100mL containers for mixture storage
  • Scale
  • 500 mL beaker
  • Funnel
  • Weigh Scale

1

Provide a detailed drawing of the laboratory or pilot area in which the work will be performed. Include locations of the experimental equipment, safety equipment (including eyewash stations and safety showers, fire extinguishers, first aid kids, noting the date(s)of last inspection of these safety devices), Safety Data Sheet(MSDS) compilation, chemical storage, and evacuation route.

1

Provide a step-wise procedure that describes in detail how the work will be performed. The procedure should begin and end with the equipment in the normal idle (inoperative) state.

Include a statement of the required PPE at the beginning of the procedure, and at every location in the procedure where the PPE requirements change.

Indicate where hazardous feedstock chemicals will be stored, how they will be transported to the location of the experimental work, how they will be transferred from storage vial into the experimental apparatus, and how they will be returned to storage.

Take into account those items for which you indicate “yes” on the NMSU Lab Hazard Assessment Checklist (link found on the department website “Safety” page).

Safety: Wear proper protective equipment including chemical resistant gloves, lab coat and safety glasses when preparing and performing this demonstration. 30% hydrogen peroxide is corrosive and a strong oxidizing agent, contact with skin and eyes must be avoided. Concentrated hydrogen peroxide can cause burns. KIO3 is an oxidizer. Malonic acid solution is moderately toxic and corrosive to eyes, skin and respiratory tract. Sulfuric acid is severely corrosive to eyes, skin and other tissue. Sulphuric acid can cause severe burns, when concentrated it is a powerful dehydrating agent and generates considerable heat when diluted with water. If spilled on to the skin, care must be exercised to avoid excessive heating when flushing with water. If you have an ice bath on hand use the water from that or you can quickly remove the bulk of the liquid with a dry cloth or tissue. Flush with plenty of water and then treat the area with sodium hydrogen carbonate (NaHCO3). Spills on the floor or bench should be neutralized with sodium hydrogen carbonate (NaHCO3)and rinsed thoroughly.The reaction produces iodine which is toxic by inhalation and irritating to eyes, skin, and respiratory tract. Perform the demonstration in a well-ventilated room.

Preparation: These should be prepared under a ventilation hood prior to the demonstration as the hydrogen peroxide loses its effectiveness over time.

  1. Solution A: Prepare 100 mL of 9% H2O2 by diluting 30 mL of 30% H2O2 with 70 mL of deionized H2O. Pour into container for transport.
  2. Solution B: Prepare an acidified 0.2 M KIO3 solution by adding 10 mL of 1.0 M H2SO4 to 80 mL of deionized water. Dissolve 4.3 g KIO3 in this solution and dilute to 100 mL. Pour into container for transport.
  3. Solution C: Prepare starch solution by dissolving 0.1 g of soluble starch in 90 mL of boiling deionized water. When cool, add 1.5 g malonic acid, 0.4 g MnSO4•H2O, stir and dilute to 100 mL. Pour into container for transport.

Demonstration:

Add 100 mL of Solution A to a clean 500 mL beaker on the magnetic stirrer fitted with a stir bar. Next, add 100 mL of Solution B and adjust the stirring rate to produce a vortex in the mixture. Once complete, add 100 mL of Solution C and let reaction stir. Upon addition of the final solution, bubbles should appear. The solution will turn yellow then blue, then colorless. This reaction will oscillate for 5-10 minutes with a period which initially lasts 15 seconds but will gradually lengthen. The reaction is complete when the solution remains blue-black.

Storage and Transportation:

The solutions are to be stored in sealed glass bottles and used at the time of demonstration. Storage over long periods is not recommended because the concentrated hydrogen peroxide will lose effectiveness over time. They can be transported in any container that does not allow them to break and spill.

Clean Up:

Neutralize the iodine by reducing it to iodide. Add ~4 g sodium thiosulfate to the mixture. Stir until the mixture becomes colorless. The reaction between iodine and thiosulfate is exothermic and the mixture may be hot. Once cool, the neutralized mixture may be washed down the drain with water.

1

Provide a step-wise procedure that describes how the equipment will be brought to a safe state in the event of an emergency. The description should include a detailed explanation of how to attend to potential medical emergencies that may result.

  1. Heated stirring plate – Turn off the heat and turn of the stirrer.
  1. Place all glass in an appropriate transportation storage area.
  1. Neutralize the iodine by reducing it to iodide. Add ~4 g sodium thiosulfate to the mixture. Stir until the mixture becomes colorless. The reaction between iodine and thiosulfate is exothermic and the mixture may be hot. Once cool, the neutralized mixture may be washed down the drain with water.

1

Prepare a Waste Management Procedure that provides the exact nature and estimated volumes of all wastes to be generated in performing these experiments. Forward to EH&S Environmental Affairs Manager, Andrew Kaczmarek for approval.

Attach a copy of the approval received from EH&S to this section of the ESP.

1.) Waste Chemical Waste – After the demonstration and the mixture is neutralized with sodium thiosulfate it can be disposed of down the drain to the city sewer. The drain should be washed thoroughly.

2.) KIO3 powder spill on weigh scale - Sweep up, then place into a suitable container for disposal.

1

Identify ALL HIGH hazards associated with the experiment. The analysis must consider

  • all sources of energy (electric, chemical, hydraulics, mechanical, compressed gases),
  • extreme conditions of pressure or temperature (from flame or steam to cryogenics),
  • chemical storage,
  • housekeeping,
  • fire, and/or
  • biological hazards.

Examples of High hazards to include (list not exhaustive):

  • substances that are highly reactive, radioactive, highly flammable, pyrophoric, highly toxic, mutagenic, teratogenic, carcinogenic, orhave very low exposure limits,
  • high voltage, high RF, x-ray, laser (class 3b or 4),
  • high temperatures, and
  • high pressure or pressurizing vessels.

When in doubt about whether a substance represents a HIGH HAZARD, ask for assistance.

For each HIGH hazard (use the checklist as a guide to identifying these hazards, chme.nmsu.edu/files/2013/11/Lab-PPE-selection1.pdf), provide the following information:

  1. description of the HIGH hazard;
  2. operational and engineering controlsthat will be used
    (based on identified industry best-practices used in addressing this safety hazard);
  3. required PPE(beyond minimum) when this HIGH hazard is present; and
  4. special training (beyond minimum) that is necessary.

1.) Small volume of corrosiveliquids - 30% hydrogen peroxide is corrosive and a strong oxidizing agent, contact with skin and eyes must be avoided. Concentrated hydrogen peroxide can cause burns. KIO3 is an oxidizer. Malonic acid solution is moderately toxic and corrosive to eyes, skin and respiratory tract. Sulfuric acid is severely corrosive to eyes, skin and other tissue. Sulphuric acid can cause severe burns, when concentrated it is a powerful dehydrating agent and generates considerable heat when diluted with water. If spilled on to the skin, care must be exercised to avoid excessive heating when flushing with water. If you have an ice bath on hand use the water from that or you can quickly remove the bulk of the liquid with a dry cloth or tissue. Flush with plenty of water and then treat the area with sodium hydrogen carbonate (NaHCO3). Use safety glasses, chemical-resistant gloves, and lab coat.