Parr Instrument 1356 User Manual

No. 434M

1356 ISOPERIBOL BOMB CALORIMETER

Service Manual

1. Calorimeter Operation

Operation……………………………………………………………………5
Corrections Fixed………………………………………………………… 6
Corrections and Final Report
Data Entry
Report Option …………………………………………………………… 7
Generate Report……………………………………………………………. 7
Display Reports …………………………………………………………… 8
Clear Memory
Edit Memory
Calorimeter Standardization ………………………………………………9
Heat of Combustion Calculation ………………………………………… 9
Calculations ……………………………………………………………….. 9
Correction Thermochemical……………………………………………….. 9
Details Thermochemical Calculation ……………………………………. 10
Sample Spiking ……………………………………………………………. 10
Spiking Sample Calculations ……………………………………………….11
Sample handling ………………………………………………………….12

2. 1108 Bomb Maintenance and Safety Instructions
Bomb Maintenance ……………………………………………………….. 11
500 Firings…………………………………………………………………. 11

3. Parts Replacement

Motor………………………………………………………………………. 14

Battery…………………………………………………………………….. 14
Cover adjustment………………………………………………………….. 14
Thermistor………………………………………………………………….. 15
Controller………………………………………………………………… 15

Controller Combined …………………………………………………….. 15
Keyboard
Cover Replacement………………………………………………………. 16
Support Rod ………………………………………………………………. 17

4. Error Messages
Preperiod/Postperiod

Misfire …………………………………………………………………… 19
Exceeded Calibration Limit………………………………………………. 19
Oxygen Charge Low……………………………………………………… 19

5. Miscellaneous
Misfire-wire intact

1356 Precison
Calculate Tests per Oxygen Cylinder

Volatile Spiking
Sulfuric acid correction …………………………………………………… 21
Use of inert gas-heat capacity
ISO/BSI corrections

…………………………………………………………………. 7

………………………………………………………………8

………………………………………………………………. 8

………………………………………………………………….. 16

……………………………………………………. 18

………………………………………………………… 19

……………………………………………………………… 20

…………………………………………………………… 21

……………………………………………………… 23

………………………………………………. 7

…………………………………….. 20

…………………………………………….. 22

MSDS sheet benzoic acid…………………………………………………. 41
Data Logger 1356 ………………………………………………………… 24
Screen Bubbles ……………………………………………………………. 24
Stirrer Harness A1573E2………………………………………………….. 24
Replacing LCD Display and Keypad……………………………………. 25
Replacement I/O Board ……………………………………………………. 25
Longer Post Periods
Power Supply Board Replacement
CPU Board Replacement………………………………………………….. 27

6. Parts
5 year………………………………………………………………………. 27
Parts Information
5000 tests
Assembly Hinge ………………………………………………………….. 29
1563 Water Handling……………………………………………………… 30

7. Diagrams

Front View 1356 Calorimeter…………………………………………….. 32
Upper Link…………………………………………………………………. 33
Lower Link………………………………………………………………… 33
Left Linkage Bracket ……………………………………………………… 34
Right Mounting Plate ………………………………………………………35
Left Mounting Plate……………………………………………………….. 35
Right Linkage Bracket…………………………………………………….. 36
Cover Assembly 1356…………………………………………………. 37
Hinge Assembly…………………………………………………………… 37
1563 Flow Diagram……………………………………………………….. 38
1563 Electrical Diagrams………………………………………………….. 39

………………………………………………………………… 28

………………………………………………………. 25

……………………………………….. 26

………………………………………………………….. 27

4

1. Calorimeter Operation

A. Operating the Calorimeter

All operations required to standardize the Calorimeter, or test an unknown sample, should
proceed step-wise in the following manner:

1. Turn on the calorimeter, go to menu page 1 and press YES key on line 3 to
activate the pump and heater.. The bomb parts should be wetted and then dried in
the manner used at the conclusion of a test. This serves to wet all sealing parts, as
well as leaving the bomb with the same amount of residual water which will exist
in all subsequent testing.

Prepare the sample and charge the oxygen bomb by attaching the hose to the

bomb and pressing the O2 Fill key.

The throughput of the 1356 Calorimeter can be increased by using multiple

bombs and water buckets. With this arrangement, the calorimeter can operate
almost continuously since the operator will be able to empty a bomb and recharge
it while a run is in progress. A bomb and bucket for the next run will be ready to
go into the calorimeter as soon as it is opened. Each bomb and bucket
combination will have to be standardized separately and the proper energy
equivalent for each set must be used for the heat of combustion calculation.

2. Fill the calorimeter bucket by first tarring the dry bucket on a solution or trip
balance; then add 2000 (+/- 0.5) grams of water. Distilled water is preferred, but
de-mineralized or tap water containing less than 250 ppm of dissolved solids is
satisfactory. The water temperature should be approximately 1 to 2ºC below the
room temperature. It is not necessary to use exactly 2000 grams, but the amount
selected must be duplicated within +/-0.5 gram for each run. Instead of weighing
the bucket, it can be filled from an automatic pipette, or from any other
volumetric device if the repeatability of the filling system is within +/-0.5 ml. Try
to make the starting temperature as repeatable as possible.

3, To speed and simplify the bucket filling process, and to conserve water and

energy, Parr offers a closed-circuit Water Handling System (No. 1563). This
provides a water supply, cooled to the starting temperature and held in an
automatic pipette ready for delivery in the exact amount needed to fill the bucket.
A 1552 Water Cooler is required when using the 1563 Water Handling System.
Instructions for this automatic system are given in Operating Instruction No. 245
and 246M.

4. Set the bucket in the calorimeter. Attach the lifting handle to the two holes in the
side of the screw cap and partially lower the bomb in the water. Handle the bomb
carefully during this operation so that the sample will not be disturbed. Push the
two ignition lead wires into the terminal sockets on the bomb head. Orient the
wires away from the stirrer shaft so they do not become tangled in the stirring
mechanism. Lower the bomb completely into water with its feet spanning the
circular boss in the bottom of the bucket. Remove the lifting handle and shake any
drops of water back into the bucket. Check for any bubbles coming from the
bomb, if bubbles are seen, do not fire the bomb. Resolve the problem.

5. Close the calorimeter cover

5

Press the START key . The calorimeter will prompt for a Cal ID. The calorimeter
will then prompt for sample identification number by displaying Sample ID on
the display. Enter the correct sample ID by using any number, up to six digits, to
identify the sample. The calorimeter will check its memory and will not accept
duplicate sample ID numbers. Enter this value. The system will now prompt for a
sample weight, enter the sample wieght.

6. The calorimeter will now take over and conduct the test. During the time it is
establishing the initial equilibrium, it will display the PRE-PERIOD. Once the
bomb has been fired, the POSTPERIOD will be displayed. The calorimeter will
check to make certain that a temperature rise occurs and will then look for the
final equilibrium conditions to be met. If it fails to meet either the initial or final
equilibrium conditions, or if it fails to detect a temperature rise within the allotted
time, the calorimeter will terminate the test and advise the user of the error.

7. At the conclusion of the test, the calorimeter will signal the user and print the
results.

8. Open the cover, detach the lead wires from the bomb and remove the bucket with
the bomb. Remove the bomb from the bucket and open the knurled valve knob on
the bomb head to release the residual gas pressure before attempting to remove
the cap. This release should proceed slowly over a period of not less than one
minute to avoid entrainment losses. After all pressure has been released, unscrew
the cap, lift the head out of the cylinder and place it on the support stand.
Examine the interior of the bomb and fuel capsule for soot or other evidence of
incomplete combustion. If such evidence is found, the test will have to be
discarded.

9. Wash all interior surfaces of the bomb with a jet of distilled water and collect the
washings in a beaker.

10. Use Fixed Corrections or remove all unburned pieces of fuse wire from the bomb
electrodes; straighten them and measure their combined length in centimeters.
Subtract this length from the initial length of 10 centimeters and multiply this
burned length by 2.3 calories per cm (for Parr 45C10 Fuse Wire) to obtain the
fuse correction. The scale on the fuse wire card can be used to obtain this value
directly. If fixed corrections are used no entry is required.

11. Use fixed corrections or titrate the bomb washings with a standard sodium
carbonate solution using methyl orange, red or purple indicator. A 0.0709N
sodium carbonate solution is recommended for this titration to simplify the
calculation. This is prepared by dissolving 3.76 grams of Na2CO3 in the water and
diluting to one liter. NaOH or KOH solutions of the same normality may be used.
Enter the titer value for the acid correction. If fixed acid corrections has been
programmed, no entry is required.

12 Analyze the bomb washings to determine the sulfur content of the sample if it
exceeds 0.1 percent. Methods for determining sulfur are discussed in Operating
Instructions No. 207M.

13. Turn off the calorimeter at the power switch.

6

B. Entering Corrections and Obtaining the Final Report

Final reports for each test can be obtained via the REPORT key, whenever the user is
prepared to enter the corrections for acid, sulfur and fuse.
Refer to the Reporting Generation for the steps necessary to initiate a report from the
calorimeter.

C. Manual Entry

During the reporting process, the calorimeter will prompt the user to enter the following
values:
Fuse Correction: Key in the Fuse Wire Correction and press the ENTER key. The default
setting for this value is to be entered in calories.
Acid Correction: Key in the Acid Correction and press the ENTER key. The default
setting for this value is to be entered in milliliters of standard alkali required to titrate
total acid or calories.
Sulfur Correction: Key in the Sulfur Correction and press the ENTER key. The default
setting for this value is entered as percent sulfur in the sample.
Enter these values when requested by the corresponding prompt. After the last entry has
been made, the calorimeter will automatically produce a final report. If values for these
corrections are not available, the user can use the SKIP key to pass over any of these
corrections. However, a final report will not be printed until an entry is made for each of
the three correction factors.

D. Fixed Corrections

In many cases, fixed values for fuse and acid can be used without introducing a
significant error since the corrections are both relatively small and constant. Fixed sulfur
corrections can also be used whenever a series of samples will be tested with a
reasonably constant sulfur content. Details for applying fixed corrections are found in the

Details Thermochemical Calculation Any value setup as a fixed correction will be

automatically applied and the calorimeter will not prompt the user for this value.

E. Report Option Selection

Data can be transferred over the RJ45 port to a 40 or 80 column printer to provide a
printed report. This port can also be used to transmit data to a host computer. In this case,
the data will have to be received, stored and formatted by programs residing in the host
computer. If you wish to transfer data to a computer ask for software from Parr, we can
quote a price for the software.
The default setting sends the calorimetric reports to the printer.

F. Report Generation

There are two kinds of calorimeter reports, which can be issued; preliminary and final.
Preliminary reports are generated at the conclusion of a test run when one or more of the
calorimeter corrections (FUSE, ACID, SULFUR, SPIKE) is not fixed. A final report
contains all of the final or fixed calorimetric corrections needed in order to give either an
energy equivalent or heat of combustion value.

7

Reports may be obtained by pressing the REPORT key. To obtain a block of reports
between two specified sample numbers, press the REPORT key. Enter the first sample
number to the display, and press the ENTER key. The system will then prompt for the
last sample ID, if only one report is desired enter the same sample ID, followed by the
ENTER key. If a block of reports is desired enter the last sample in the block followed by
the ENTER key. During the reporting process, the printed reports will indicate whether
the reports are final or preliminary. The preliminary reports will require corrections to be
entered.
Preliminary reports will remain preliminary and the energy equivalent or heat of
combustion value, which is reported will reflect the fixed constants as set by the operator.
The printing of large numbers of reports may be avoided at any time using the RESET
key. The reset action will take effect after the current report has been completely
transmitted.

G. Displayed Reports

Reports may also be obtained through the display on the 1356 Calorimeter. The
procedure for obtaining reports on the display is the same as for obtaining printed reports.
The calorimeter will hold data for 500 tests within its memory. These tests may be either
preliminary, final, determination or calibration reports. Once the memory of the
calorimeter is filled, any attempt to start a new analysis will cause the calorimeter to
display MEMORY FULL, to avoid this error message go to Menu page 7 and line 6.
Change the Overwrite from OFF to On, then the oldest test will be deleted and replaced
by the most recent test. The alternative is to clear memory of tests.

H. Clearing Memory

This capability allows the user to delete Sample ID numbers and all related data and
results for a single report, a sequence of reports or for all reports.
To clear a single report, press the CLEAR MEM key. The calorimeter will prompt for the
first sample number in the block and then prompt for the last sample number in the block,
then press the ENTER key. To clear all reports, use the sequence procedure with 1 as the
first sample number and 999999 as the last number of the sequence.

I. Editing Memory

The user is able to add data and information to the previously gathered information for a
test by using the Memory Editing procedures described in the manual on page 8-1.
Press the F3 key. The calorimeter will then prompt for the first sample number, which is
keyed in and press the Enter key. The calorimeter will then prompt for the las t sample
number in the block, enter the ID and press the Enter key. If one wishes to edit one
sample, then enter the same number for the first and last sample ID. Highlight the data
field to be edited by pressing the Up or Down Arrow key

8

Press the Clear key, enter the new value on the keyboard and press the Enter key. This
sequence is canceled by pressing the RESET key. Press the Escape key, when one is
done editing. If more than 1 sample is to be edited, the screen will display the next
sample’s information.

J. Standardizing the Calorimeter

The calorimeter will calculate the average EE value from standardization tests that have
been made.

K. Calculating the Heat of Combustion

While the Model 1356 Calorimeter will automatically make all of the calculations
necessary to produce a gross heat of combustion for the sample. It is important that the
user understand these calculations to ensure that the instrument is set up so that the
calculations match the procedures used and that the units are consistent throughout the
entire procedure and calculations.

L. General Calculations

Basically, the calculation of the gross heat of combustion is done using the following
equation:
Where:
Hc =Gross heat of combustion.
T =Observed temperature rise.
EE =Energy equivalent of the calorimeter being used.
e1 =Heat produced by burning the nitrogen entrapped in the bomb to form nitric acid.
e2 =Extra heat produced due to burning sulfur to sulfur trioxide and forming sulfuric
acid instead of sulfur dioxide.
e3 =Heat produced by the burning fuse wire.
m =Mass of the sample.
For convenience and by tradition, these calculations are made in calories, grams,
and degrees Celsius, and then converted to other units if required. The other units desired
are set on Menu page 2, line 2.
Temperature rise
automatically. Corrections for heat leaks are applied automatically. Similarly, the method
for extrapolating the end point of the test is discussed in the dynamic method description.
Energy equivalent
abbreviated as EE) is determined by standardizing the calorimeter as described in the
Standardization Section of the calorimeter manual. It is an expression of the amount of
energy required to raise the temperature of the calorimeter one degree. It is commonly
expressed in calories per degree Celsius. Since it is directly related to the mass of the
calorimeter, it will change whenever any of the components of the calorimeter (i.e. the
bomb, bucket, or amount of water) is changed.

M. Thermochemical Corrections

Nitric acid correction

. The 1356 Calorimeter produces a corrected temperature rise reading

. The energy equivalent (represented by W in the above formula, or

. In the high pressure oxygen environment within the oxygen bomb,

9

nitrogen that was present as part of the air trapped in the bomb is burned to nitric oxide
which combines with water vapor to form nitric acid. All of this heat is artificial since it
is not a result of the sample burning.
Sulfur correction. In the oxygen rich atmosphere within the bomb, sulfur in the sample is
oxidized to sulfur trioxide, which combines with water vapor to form sulfuric acid. This
liberates additional heat over the normal combustion process, which converts sulfur to
sulfur dioxide. The sulfur correction removes this excess heat from the calculations.
Fuse wire correction. The wire used for a fuse to ignite the sample is partially consumed
in the combustion. Thus, the fuse generates heat both by the resistance it offers to the
electric firing current and by the heat of combustion of the wire that is actually burned. It
is normally assumed that the heat generated by the electrical resistance will be the same
when standardizing the bomb and when testing an unknown sample, and can therefore be
ignored. Significant variances can, however, occur in the amounts of fuse wire actually
burned in each test. So this energy is subtracted to account for the heat of combustion of
the metal.

N. Thermochemical Calculation Details

Traditionally, standard solutions and procedures have been established to simplify the
calculations and thermochemical calculations.

ACID and SULFUR Corrections. In certain ASTM methods, the amount of sodium
carbonate used to titrate the bomb washings is equated with e1.
Users may find it convenient to enter a fixed value for the acid correction and avoid the
need to determine this correction for each test. To enter Fixed Acid Corrections,go to
Menu page 5 and turn on line 1 Fixed Fuse for Standardization or line 4 for
Determination. Total errors of more than 3 calories will seldom occur when using Fixed
Acid Corrections.
Fixed Sulfur Corrections can be entered if a series of samples contain a constant amount
of sulfur. For Standizations, line 3 is always ON. For determination runs to enter Fixed
Sulfur Corrections, turn on Line 6 and enter the estimated value.

O. Spiking Samples

It is sometimes necessary to add a spiking material to samples, which are very small,
have a low heat of combustion, or have a high moisture content to add sufficient heat to
drive the combustion to completion. Benzoic acid is an excellent material for spiking for
all of the same reasons that it is a good standard material. White oil is also an excellent
material; particularly for liquid samples. The 1356 Calorimeter can automatically
compensate for the addition of spiking materials to these samples.
When Use Spiking is turned on, on Menu page 2.3 and line 1, the heat of combustion of
the spiking material must be entered on Menu page 2.3, line 2.
During data entry when using a spike, the calorimeter will prompt for both the sample
weight and the spike weight.

10

Spiking Calculations

[{EE x T(temp rise)}-e1-e2-e3-[mass(oil) x Heat Combustion(oil)]/sample m grams

2. 1108 Oxygen Bomb Maintenance and Safety Instructions

Oxygen Bomb Maintenance

Under normal usage Parr oxygen bombs will give long service if handled with reasonable
care. However, the user must remember that these bombs are continually subjected to
high temperatures and pressures which apply heavy stresses to the sealing mechanism.
The mechanical condition of the bomb must therefore be watched carefully and any parts
that show signs of weakness or deterioration should be replaced before they fail.
Otherwise, a serious accident may occur.

Do not fire the bomb if gas bubbles are observed anywhere indicating a possible gas
leak. Disassemble the parts and install new seals immediately.
Keep the 397A compression nut on the valve needle tightened firmly at all times.

Frequent tightening is important. This nut, if slightly loose, may allow a leak to develop
during the rapid pressure rise upon ignition. This type of leak may not be detectable
before firing; but if it develops, the hot gases can ignite the 20VB valve seat and burn
through the head.
Do not use extreme force when closing the needle valve. A moderate but firm turn on
the valve knob should be sufficient to stop all gas flow. Excessive needle pressure will
deform and possibly close the gas passage. If this happens, unscrew the valve body and
replace the 20VB valve seat. Accumulated salt deposits may also clog the gas passage,
making it difficult to release pressure at the end of a run. To avoid this, clean the passage
through the valve needle and deflector nut with a small drill.

Firings 500

All O-rings and 20VB valve seats should be replaced after 500 firings for the standard
1108 Oxygen Bomb and 250 firings for the 1108CL Oxygen Bomb for chlorine content
of samples is 25% or greater.
A Parr 475A service clamp offers a convenient means for clamping the bomb head firmly
in a vise without damaging the head when replacing any of the bomb head parts.
When replacing the 230A head gasket, stretch the new O-ring and let it snap into place to
be sure that it moves freely in its groove and is not twisted.
To replace the valve seat, unscrew the 397A compression nut; remove the valve stem and
the old seat, and disassemble all of the parts. Drop a new 20VB valve seat into the body
and push it down into place. Slide a 7VBCM Monel washer, two 238A O-rings and
the 378A packing cup onto the valve needle with the needle pointed upward; then adjust
the parts on the needle so that the tip of the needle is flush with or slightly recessed into
the bottom of the packing cup. Insert this assembly into the 369A outlet valve body and
press it firmly against the valve seat by tightening and 397A compression nut to 100
inch-pounds of torque.
The 238A sealing ring in the insulated electrode should be replaced with the same
frequency as the 20VB valve seat. Also keep the 411A terminal nut tight at all times. As

11

Sample preparation

12

the 238A sealing ring ages and hardens it becomes a partial electrical conductor,
permitting misfires and producing unwanted heating effects. Periodic replacement will
eliminate this potential problem.
The threads on the screw cap should be checked routinely for any burrs or other
deformity. After long use, the threads on the screw cap may become worn to the point
where they will no longer provide a safe closure for the bomb, and the screw cap will
have to be replaced. The following procedure can be used to check the extent to which
the threads have become worn.

Assemble the bomb with the head in the cylinder and count the number of turns required
to bring the screw cap down firmly against the head. Then open the bomb; remove the
head and replace the screw cap, but turn it down to only one-half of the turns previously
counted. This will usually be about four turns. With the screw cap in this position, use a
dial gage to measure the vertical deflection when lifting the screw cap upward. If this
measurement exceeds 1/32 inch (0.030”), the screw cap is unsafe and should be
discarded. The cylinder can then be returned to the factory for inspection. If the threads
on the cylinder are in good condition, a new screw cap can be custom-fitted to the
cylinder.

Never under any circumstances use oil on valves or fittings which handle
compressed oxygen. This precaution applies to all of the oxygen bomb parts as well as to

the oxygen filling connection.

The 1108CL Bombs will resist chlorine, fluorine or bromine in the presence of moisture.
If samples yielding appreciable amounts of these elements are burned in a Parr bomb, the
bomb should be emptied and washed as quickly as possible after each combustion.
If the interior of the bomb cylinder should become etched, the resistance of the metal to
further attack can be improved by restoring the surface to its original highly polished
condition. Bombs needing polishing or other repair work can be returned to the factory.
A periodic overhaul and test at the factory will help to keep any Parr oxygen bomb in
first-class condition.

Parr oxygen bombs can be returned at any time for repair and testing. A factory test is
recommended after every 5000 firings, or sooner if the bomb has been subject to any of
the following conditions: (a) fired with an excessive charge, (b) ignition of any internal
components, (c) machined by any source other than the factory, (d) damaged by corrosive
vapors that might have exceeded 80% of the corrosion allowance, or (e) any changes in
the threads on the bomb cylinder and/or screw cap. When returning a bomb to the
factory, ship it to Parr Instrument Company, 211-53rd Street, Moline, Illinois 61265, with
the package marked for the attention of the Repair Department. A purchase order
covering the repair work should be included with the shipment or mailed to the same
address, as no repairs will be started without specific instructions. Be sure to include a
return shipping address and the name and telephone number of the individual to be
contacted if questions arise concerning excessive repair costs or other problems.
Individual repair parts can be ordered from any Parr dealer or direct from the factory.

13