Experimental Methods and Instrumentation for Chemical Engineers

Montréal

Preface

Throughout the day, we apply experimental methods to estimate time, mass, volume, distance, velocity, and temperature—how much to eat (mass), what clothes to wear (temperature), how long will it take to get somewhere (distance, velocity, and time). Preparing a meal requires some precision with respect to these factors, and the kitchen was the first laboratory for chemists and engineers. We continue to share many concepts related to instrumentation and experimental design. This book presents the basic principles of measurement particular to chemical engineering. Redacting this manuscript has been a collaborative effort; its original inspiration was J.P. Holman's textbook entitled Experimental Methods for Engineers. In this 2nd edition, we revise the text entirely, correct typos (and other errors), and add a chapter on mass and distance and spectroscopy.

Each chapter begins with a historical perspective to recognize the work of early pioneers but also to stimulate the imagination of the students. For example, 10 000 years ago, man created plaster from limestone. Plaster requires temperatures nearing 900°C, which is 150°C higher than an open pit fire. It requires 1000 kg of wood (chopped by stone axes), 500 kg of limestone, a pit 2 m in diameter and 0.7 m deep, rocks to insulate, and two days to burn. Modern manufacturing errors are costly and a nuisance; in prehistoric times, errors would have been considerably more than just an inconvenience.

In Chapter 1, we list the seven steps of the scientific method and review the rules of nomenclature—units of physical quantities, abbreviations, conversion between SI and British Units, writing convention. Chapter 2 introduces significant figures and what we mean by accuracy, precision, and error analysis. In this second edition, we report an explicit equation to calculate how many experiments are necessary to achieve a specified confidence interval.

Chapter 3 reviews data analysis including hypothesis testing, data smoothing, and statistical tests. We summarize design of experiments, and we include more detail in this edition to describe factorial designs, outlining them and other complementary designs with detailed examples.

Chapter 4 is new and introduces stress, strain, and electrical properties that relate to manufacturing sensors for mass and force. We apply these concepts in Chapters 5 and 6 that deal with pressure and temperature measurements. In each of these chapters, we first review basic concepts, including thermodynamics. Then we describe the sensors that rely on mechanical and electrical properties.

Chapters 7 and 8 continue with chemical engineering fundamentals of fluid flow and physicochemical properties. The former begins with Bernoulli's equation and Reynolds number, then lists common flow meters. The three physicochemical properties that Chapter 8 presents include viscosity, thermal conductivity, and diffusion. It demonstrates how these properties are related and introduces non-dimensional numbers.

Examples throughout the book help the students grasp the mechanics of solving problems but also to underline pitfalls in solving them.

Measuring gas and liquid concentration by chromatography and mass spectrometry is the subject of Chapter 9. In this edition, we dedicate more scope to troubleshooting the chromatographic instruments. Spectroscopic instruments we detail in Chapter 11. This summary includes sections written by eminent chemists. We have selected the most powerful techniques used to characterize the physicochemical properties of solids and include infrared spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, nuclear magnetic resonance, UV/Vis, X-ray absorption, and refractometry

Whereas Chapter 11 probes the nature of the solids phases, composition and morphology, Chapter 10 concentrates on powder properties—particle shape, size distribution, density, and surface area.

The first edition of this book was a collaborative effort in which Melina Hamdine early on drafted several chapters in French, including Physicochemical Properties, Analysis of Powders and Solids, and Design of Experiments. Prof. Bala Srinivasan contributed to Chapter 3 on experimental design. Katia Senécal was instrumental in gathering the essential elements for the chapters, including Measurement Analysis, Pressure, Temperature, and Flow Rate. Prof. Bruno Detuncq collaborated in the revision of these chapters. Danielle Béland led the redaction of the chapter on chromatography to determine concentration, with some assistance from Cristian Neagoe. He also wrote the section concerning spectroscopy. Amina Benamer contributed extensively to this project, including preparing solutions to the problems after each chapter, writing sections related to refractometry and X-ray, and translating. Second-year students from the Department also participated by proposing original problems that were added at the end of each chapter (together with the name of the author of the problem). I would particularly like to recognize Paul Patience for his tremendous contribution throughout the creative process of preparing this manuscript. The depth of his reflection has been appreciated tremendously (LATEX). He also co-authored the section on pyrometry. Christian Patience prepared many of the drawings and Nicolas Patience helped with translating from French to English, as did Nadine Aboussouan.

This second edition is no less a collaborative effort. Ariane Bérard expanded Chapter 3 with examples of experimental designs. Prof. J. Gostick contributed the chapter on Mass and Force instrumentation. Stefano Lucini wrote the section on troubleshooting GC and HPLC instruments, while F. Galli contributed to the section on mass spectrometry with Patrice Perreault, who was devout at identifying errors and proposing additional problems. Marco Rigamonti and He Li wrote sections of Chapter 10. Collaborators on Chapter 11 included Daria C. Boffito, Cristian Neagoe, Giuseppina Cerrato, Claudio Boffito, Gian Luca Chiarello, Claudia L. Bianchi, Marco G. Rigamonti, and Amina Benamer. This chapter is a tremendous contribution to the book because it details simply which instruments measure which physicochemical property and then describes how they work.

Chapter 1

Introduction

G.S. Patience    Polytechnique Montréal

Abstract

The introductory chapter reviews writing conventions, units of physical quantities, metrology as well as the importance of quality control in an industrial setting. From a historical perspective, experimental methodology has been a prime factor in the development of technology. The notions of time, mass, and length (T, M, L) have been well understood for thousands of years (many moons) but standardization—adoption of the SI system, for example—dates back only 200 years. Besides T, M, and L, the other base units that make up SI include amount of matter (N, moles), temperature (θ), luminous intensity (J), and electrical current (I). Together with ISO—International Organization for Standardization—many other international and national organizations have been formed to oversee quality in many fields. Some of the more famous institutions include the ASTM (American Society for Testing and Materials), BSI (British Standards Institute), and SAE (Society of Automotive Engineers).

Keywords

Experimental methods; Instrumentation; Sensors; ISO—International Organization for Standardization; Metrology; SI—Système International d'Unité; Writing conventions; Time; Mass; Distance

Overview

Experimental methods and instrumentation—for the purpose of systematic, quantifiable measurements—have been a driving force for human development and civilization. Anthropologists recognize tool making, together with language and complex social organizations, as a prime distinguishing feature of Homo sapiens from primates and other animals. However, the animal kingdom shares many practices characteristic of experimentation, instrumentation and innovation. Animals measure distance, height, size, estimate probabilities and adapt objects for tasks: cheetahs, for example, gauge distance between themselves and their prey before giving chase. Several species devise tools: branches are levers for large arboreal primates that travel through the forest from tree to tree; chimpanzees modify sticks as implements to extract grubs from logs; beavers cut down trees and use mud and stones to build dams and lodges; and, Betty the crow bends a wire to make a hook to get food out of a narrow tube. If the act of modifying a twig to extract grubs is considered tool making then we need a more specific definition to differentiate humans from other species. Man uses tools to make tools and adopts a methodology to improve an outcome or function. One of the earliest examples of applying methodology is when early hominids manufactured chopping and core tools—axes and fist hatchets—before the Lower Paleolithic period (from 650 000 to 170 000 BC): they produced blades and implements by cleaving rocks with a certain force at a specific angle to produce sharp edges. The raw material—a rock—is modified through the use of an implement—a different rock—to produce an object with an unrelated function (cutting, scraping, digging, piercing, etc.). Striking rocks (flint) together led to sparks and the discovery of how to make fire.

Throughout the day, we measure mass, size, time, temperature and use instruments. The clothes that we wear, the food that we eat, the objects that we manipulate have all been developed and optimized with standardized procedures and advanced instrumentation. Sensors have increased the efficiency and safety of automobiles: gauges in the car assess gasoline/air ratio, rain on the windshield, cabin temperature and whether or not the seat belt is engaged. One of the key factors in homes is maintaining the correct temperature either in rooms, refrigerators, hot water heaters, ovens, or elements on the stove. Advanced scales display body mass, percent fat, and percent water!

Technological development recognizes and applies unrelated or non-obvious phenomena to new applications or to improve existing applications. Advancing technology is achieved through systematic experimental design, trial-and-error testing, or by accident. Man interprets our environment with the five+ senses —sight, sound, smell, touch, hearing, time, nociception, equilibrioception, thermoception—and each has had a historical role to innovate and devise tools.

The manufacture of primitive stone tools and fire required a qualitative appreciation for the most common measures of mass, time, number, and length. The concept of time has been appreciated for thousands of years. In comparative terms it is qualified by longer and shorter, sooner and later, more or less. Quantitatively, it has been measured in seconds, hours, days, lunar months, and years. Calendars have existed for well over 6000 years and clocks—instruments to measure time intervals of less than a day—were common as long as 6000 years ago. Chronometers are devices that have higher accuracy and laboratory models have a precision of 0.01 seconds.

The Egyptians were among the first to tell time over the entire day: 10 hours during the daylight, 12 hours at night, and 1 hour at dawn and dusk—the shadow hours. They could tell time at night based on the position of the stars in the sky. During the same period, Babylonians, Chinese, Greeks, and Romans had sun dials to tell time. The Egyptians replaced star gazing with a water clock (clepsydra) to tell time at night: Prince Amenemhet filled a graduated vessel with water and pierced a hole in the bottom to let the water drain (Barnett, 1998). Records of the hourglass date back to the early 13th century. Burning candles and incense sticks predated the hourglass.

Recording time requires a numbering system and something to detect a change in quantity. In the simplest form of the water clock, Egyptians read time based on the liquid level in a vessel as indicated by a notch on the side. Notches on bones, wood, stone, and ivory to keep records—tally sticks—date before the Upper Paleolithic (30 000 BC). Medieval Europe relied on this system to record trades, exchanges, and even debt, but it was mainly for the illiterate. Courts accepted tally sticks as legal proof of a transaction. Western civilization continues to use tally marks to update intermediate results. This unary numeral system is written as a group of five lines: the first four run vertically and the fifth runs horizontally through the four.

The driving forces to maintain records and develop numbering systems in ancient civilizations were for taxes, lending, land surveying, and irrigation. The earliest written records of metrology come from Sumerian clay tablets dated 3000 BC. These tablets had multiplication tables, division problems, and geometry. The first abacus—an ancient calculator—appeared around 2700–2300 BC. Later tablets—1800–1600 BC—included algebra, reciprocal pairs, and quadratic equations (in a circle comes from the Sumerians sexagesimal numeral system (Mastin, 2010). Like the Greeks, Romans, and Egyptians, they also had a decimal system. The Pythagorean doctrine was that mathematics ruled the universe and their motto was all is number.

Metrology

Metrology is the science of measurement and is derived from the Greek words metron (measure) and logos (logic, study, calculation, and reason). The International Bureau of Weight and Measures defines it as a science that encompasses theoretical and experimental measures at any level of uncertainty in the fields of science and engineering. It comprises not only the instruments applied to quantify the magnitude of a physical phenomenon but also standards, procedures, quality control, training, documentation, etc. Analysis and quantification of uncertainty are core elements, as is traceability—which relates to an instrument's measurements to known standards as well as the documented accreditations to national and international standards.

Together with the physical aspects of recording data accurately and repeatedly, metrology verifies and validates data collected by the test equipment. Enforcing standards is a critical aspect not only for consumer goods—baby carriages, helmets, and the like—but also for industrial equipment such as vessel design (pressure vessels), materials of construction (quality of steel), and safety procedures.

Along with international organizations that maintain standards for the basic measures of distance, weight, etc., countries also maintain their own system of metrology (Table 1.1). For example, the National Institute of Standards and Technology (NIST), formerly the National Bureau of Standards founded in 1918, maintains both scientific and commercial metrology in the United States. Its mission is to promote American innovation and competitiveness and supplies industry, academia, and government with certified standard reference materials, including documentation for procedures, quality control, and materials for calibration. The German Institute for Standards (DIN) was founded in 1917 while in the United Kingdom the BSI was formed in 1901.

Table 1.1

Further to national standards, many industries have promoted and maintained their own standards. One of the most well-known and oldest non-governmental standards organizations is the American Society for Testing and Materials (ASTM), which was established in 1898. It collects and maintains over 12 000 standards that are available to the public and include 82 volumes (at a price of $9700 in 2010). The origin of the organization was the desire to improve the quality of the rail system that had been plagued by breaks.

Although the International Organization for Standards—ISO—is a non-governmental organization, it has the authority to set standards that become law through treaties or through the national standards organizations that are represented in the organization and have 163 member countries. It follows ten-steps to make a procedure:

1.  Preliminary work item.

2.  New work item proposal.

3.  Approved new work item.

4.  Working draft.

5.  Committee draft.

6.  Final committee draft.

7.  International standard draft.

8.  Final international standard draft.

9.  Proof of a new international standard.

10.  International standard.

Three common standards are:

•  ISO 5725 (1998–2005): Accuracy of Measurement Methods and Results Package.

•  ISO 9001 (2008): Quality Systems Management—Requirements.

•  ISO 17025 (2005): General Requirements for Calibration Laboratories.

The ISO 9001 standard was originally based on BS 5750. A primary objective of this standard is to ensure the commitment of management to quality with respect to the business as well as to customer needs. The Quality Systems Management standard recognizes that employees require measurable objectives. In addition to a detailed record system that shows the origin of raw materials and how the products were processed, it includes auditing (both internal and external, in the form of certification) at defined intervals to check and ensure conformity and effectiveness.

The standard for calibration laboratories (ISO 17025) is closely aligned with the ISO 9001 standard but includes the concept of competency. Moreover, continual improvement of the management system itself is explicitly required as well as keeping up to date with technological advances related to the laboratory.

Scientific Method

The scientific method is a structured sequence of steps to answer questions or evaluate observations. Many disciplines apply a structured approach to solve problems: a 1600 BC papyrus detailed a procedure to treat disease that started with an examination, followed by diagnosis, treatment and prognosis (Wilkins, 1992). The scientific method first asks a question or makes an observation. The second step involves background research including reading the literature. In the third step, we make a hypothesis (Chapter 3) then test the hypothesis with an experiment. Many experiments rely on instrumentation that we assemble, each of which has a degree of uncertainty. All equipment must be carefully calibrated and monitored before, during, and after the experiments to ensure that the data we collect are reproducible (Chapter 2). If they are irreproducible, then we must re-examine the experimental methodology and instrumentation. After we analyze the data, we communicate our findings by addressing the original hypothesis:

1.  Ask a question.

2.  Review literature.

3.  Formulate a hypothesis.

4.  Design and conduct experiments.

5.  Analyze the data.

a.  Evaluate reproducibility and uncertainty.

b.  Improve reproducibility and reduce uncertainty, if needed.

6.  Comment on the hypothesis.

7.  Communicate the results.

Industrial Quality Control

Industrial metrology concerns accuracy as much in the laboratory as in the field but it is more constrained in that measurements must often be made in hostile environments including high temperature, dust, vibration, and other factors. Moreover, time and financial cost are other factors. Companies implement quality control systems to account for these factors. The ability to measure accurately and consistently and then interpret the results correctly to make coherent decisions is the basis of modern manufacturing. In advanced commercial chemical installations, workstations collect thousands of independent measurements at frequencies greater than 1 Hz and store them in massive databases. Operators read data in real time through consoles in a central location. They serve to control the plant, troubleshoot, detect deviations from normal operation, analyze tests designed for process optimization, and are also a historical record in the case of accidents. Additionally, the databases may be used for environmental reporting to the authorities. Online analytical devices are less common than pressure and temperature measurements, but increase the level of confidence in operations and allow for mass balance and process performance calculations in real time—this improves product tracking and troubleshooting capabilities.

Duplicate and triplicate measurements of pressure and temperature of critical pieces of equipment improve safety. When a variable like pressure or temperature exceeds a threshold value, an alarm sounds and a reading appears on console for the operator to take action. Alarms require operators to intervene while interlocks shut the process or equipment down automatically.

In addition to redundant pressure and temperature gauges, engineers install spare pumps and control valves in parallel with the main process equipment. This allows operators to bypass and service equipment it without interrupting plant operation, thereby avoiding costly shutdowns.

lost the refractory lined bricks that insulated the metal wall from the high temperature. To avoid an unscheduled shutdown, operators sprayed cold water on the wall. This operation is clearly non-standard and introduced a potentially hazardous situation—if the water spray were inadvertently shut off, the wall temperature could increase sufficiently and perforate and result in an explosion. The chemical industry has made tremendous efforts in producing goods and services in such a way as not to impact the health and well-being of society. Before commissioning a new plant or equipment, engineers and technicians write detailed operating procedures covering all aspects of the process to ensure it operates safely.

Methodologies to assess safety hazards include: What-if, Checklist (Human Factor Checklist or General Hazards Identification Checklist, for example), Hazard and Operability Study (HAZOP), Failure Mode, and Effect Analysis (FMEA) or a Fault Tree Analysis. Together with general safety, other aspects that engineers assess include occupational health, ergonomics, fire safety, process safety, product stewardship. Instrumentation is a cornerstone to process safety management.

Units of Physical Quantities

Throughout history, civilizations have developed systems to measure weight, time, and distance. The notion of weight, or mass, emerged during the same period as counting. Local authorities defined the systems and based them on practical measures—the length of an arm, a foot, or a thumb. In the late 18th century the French National Assembly and Louis XVI commissioned the French Academy of Science to conceive a rational system of measures. The National Convention in 1793 adopted the modern standards of mass and length.

Originally, the meter was to be defined as the length of a pendulum, L, for which the half-cycle, t, was equal to 1 s:

(1.1)

where g . At the Metre Convention of 1875, the Système international (SI) was formally established and a new standard for measuring mass was created: an alloy composed of 90 % Pt and 10 % Ir that was machined into a cylinder with a height and diameter equal to 39.17 mm. Iridium was included in the new International Prototype Kilogram to increase hardness. The kilogram is the only unit based on a physical artifact and not a property of nature as well as the only base unit with a prefix.

The definition of the meter and the techniques to assess it evolved with technology. In 1799, a prototype meter bar was fabricated to represent the standard. (It was later established that this bar was too short by 0.2 mm since the curvature of the Earth had been miscalculated.) In 1889, the standard Pt bar was replaced with a Pt(90 %)–Ir(10 %) bar in the form of an X. In 1960, the standard was changed to represent the number of wavelengths of a line in the electromagnetic emission of ⁸⁶Kr under vacuum. Finally, in 1983, the standard was defined as the distance that light travels in a vacuum in 1/299 792 458 s.

The standard to measure the base unit of time—the second—has evolved as much as the standard to measure distance. During the 17–19th centuries, the second was based on the Earth's rotation and was set equal to 1/86 400 of a mean solar day. In 1956, recognizing that the rotation of the Earth slows with time as the Moon moves further away (about 4 cm y−1), Ephemeris Time became the SI standard: 1/31556925.9747 the length of the tropical year of 1900. In 1967, the second was based on the number of periods of vibration radiation emitted by a specific wavelength of ¹³³Cs.

The International System of Units (Système international d'unités or SI) recognizes seven base properties (Table 1.2)—time, length, mass, thermodynamic temperature, amount of matter, electrical current, and luminous intensity. Other measures include the plane angle, solid angle, sound intensity, and seismic magnitude and intensity. The standard changed from the cgs—centimeter, gram, second—system to SI in 1960. In 1875 at the Convention du Mètre, three international organizations were formed to oversee the maintenance and evolution of the metric standard:

•  General Conference on Weights and Measures (Conférence générale des poids et mesures—CGPM).

•  International Bureau of Weights and Measures (Bureau international des poids et mesures—BIPM).

•  International Committee for Weights and Measures (Comité international des poids et mesures—CIPM).

Table 1.2

SI Base Units

Writing Conventions

. The unit for pressure is the pascal (Pa) named after the French physicist who demonstrated that atmospheric pressure changes with elevation.

Quantities or properties are either extensive—properties that are additive for subsystems, for example mass and distance—or intensive, for which the value is system independent like temperature and pressure. Prefixes qualify the meaning of properties like specific and molar(Table 1.3). The volume occupied by 1 mol of a substance is the molar volume.

Table 1.3

SI Coherent Derived Units

The minute, hour, day and hectare are symbols that fall outside the standardized nomenclature but SI recognizes them as part of the system (. Derived unit symbols named after a person are capitalized (N—Newton, Hz—Hertz, W—Watt, F—Faraday) but they are lower case when written out (one pascal, a newton). Symbols are mathematical entities so it is incorrect to add an s to indicate plural or a period except at the end of a sentence—min. is unacceptable in the middle of a sentence. Express unit symbols in roman upright type regardless of the font.

Table 1.4

The International Bureau of Weights and Measures (BIPM—Bureau International des Poids et Mesures) (.

Roman numerals are never italicized but running numbers that represent numerical values are, like in matrices or variable subscripts (Table 1.5). Symbols representing mathematical constants like π and e are in roman but physical constants, like R(pressure P and time