CHCHE Courses (2022-23)

Lectures and recitations dealing with the principles of chemistry. First term: Chemical bonding-electronic structure of atoms, periodic properties, ionic substances, covalent bonding, Lewis representations of molecules and ions, shapes of molecules, Lewis acids and bases, Bronsted acids and bases, hybridization and resonance, bonding in solids. Second term: Chemical dynamics-spectroscopy, thermodynamics, kinetics, chemical equilibria, electrochemistry, and introduction to organic chemistry. Graded pass/fail.

Introduces the basic principles and techniques of synthesis and analysis and develops the laboratory skills and precision that are fundamental to experimental chemistry. Limited enrollment. Students entering in the academic year 2020 and before must take Ch 3 in their first nine terms of residence in order to be graded pass/fail. First-year undergraduate students entering in the academic year 2021 and thereafter must take Ch 3 in their first six terms of residence in order to be graded pass/fail. Ch 3 a and Ch 3 x both satisfy the institute's Core requirement for a Chemistry Laboratory.

Introduces concepts and laboratory methods in chemistry and materials science centered on the theme of solar energy conversion and storage. Students will perform experiments involving optical spectroscopy, electrochemistry, laser spectroscopy, photochemistry, and photoelectrochemistry, culminating in the construction and testing of dye-sensitized solar cells. Students entering in the academic year 2020 and before must take Ch 3 in their first nine terms of residence in order to be graded pass/fail. First-year undergraduate students entering in the academic year 2021 and thereafter must take Ch 3 in their first six terms of residence in order to be graded pass/fail. Ch 3 a and Ch 3 x both satisfy the institute's Core requirement for a Chemistry Laboratory.

Introduction to methods of synthesis, separation, purification, and characterization used routinely in chemical research laboratories. Ch 4 a focuses on the synthesis and analysis of organic molecules; Ch 4 b focuses on the synthesis and analysis of inorganic and organometallic molecules. Ch 4 a, second term; Ch 4 b, third term.

Modern synthetic chemistry. Specific experiments may change from year to year. Ch 5 a focuses on experiments illustrating the multistep syntheses of natural products. Ch 5 b focuses on the synthesis and spectroscopic characterization of coordination and organometallic complexes and their applications in organic and electrochemical catalysis. Methodology will include advanced techniques of synthesis and instrumental characterization. Terms may be taken independently.

Introduction to modern physical methods in chemistry and biology. Techniques include laser spectroscopy, microwave spectroscopy, electron spin resonance, nuclear magnetic resonance, mass spectrometry, FT-IR, fluorescence, scanning probe microscopies, and UHV surface methods.

Prerequisites may be waived with instructor's permission. Preference will be given to students who have taken Ch 5 a or Bi 10. This advanced laboratory course will provide experience in powerful contemporary methods used in chemical biology, including polypeptide synthesis and the selective labeling and imaging of glycoproteins in cells. Experiments will address amino acid protecting group strategies, biopolymer assembly and isolation, and product characterization. A strong emphasis will be placed on understanding the chemical basis underlying the successful utilization of these procedures. In addition, experiments to demonstrate the application of commercially available enzymes for useful synthetic organic transformations will be illustrated. Students need only attend two lab sections per week.

Introduction to methods of extraction, synthesis, separation and purification, and spectroscopic characterization of Aspirin, Tylenol, and medical test strips. Open to non-premedical students, as space allows.

Instruction in synthesis, separation, purification, and physical and spectroscopic characterization procedures of model organic and organometallic compounds. Specific emphasis will be focused on following the scientific method in the study of model organic and inorganic materials. Enrollment priority given to chemical engineering majors.

Ch 10 ab is a weekly seminar by a member of the chemistry department on a topic of current research; the topic will be presented at an informal, introductory level. Ch 10 c is a research-oriented laboratory course, which will be supervised by a chemistry faculty member. Weekly class meetings will provide a forum for participants to discuss their research projects. Graded pass/fail.

This course will introduce the Chemical Engineering discipline, career options and research opportunities through lectures and panel discussions by faculty and alumni. Graded pass/fail.

Develops the basic principles of chemical equilibrium in aqueous solutions, emphasizing acid-base chemistry, complex ion formation, chelation, solubility, oxidation-reduction reactions, and partitioning equilibria for separations.

Laboratory experiments are used to illustrate modern instrumental techniques that are currently employed in industrial and academic research. Emphasis is on determinations of chemical composition, measurement of equilibrium constants, evaluation of rates of chemical reactions, and trace-metal analysis.

Introduction to the solution of engineering problems through the use of the computer. Elementary programming in Python is taught, and applied to solving chemical engineering problems in data analysis, process simulation, and optimization. No previous knowledge of computer programming is assumed.

Atomic and molecular quantum mechanics, spectroscopy, chemical dynamics, statistical mechanics, and thermodynamics.

The synthesis, structure, and reaction mechanisms of organic compounds.

Equilibrium staged separations. Membrane separations. Absorption. Distillation. Liquid-liquid extraction. Introduction to mass transfer.

A comprehensive treatment of classical thermodynamics with engineering and chemical applications. First and second laws. Applications to closed and open systems. Equations of state. Thermochemical calculations. Properties of real fluids. Power generation and refrigeration cycles. Multicomponent systems, excess properties, fugacities, activity coefficients, and models of nonideal solutions. Chemical potential. Phase and chemical reaction equilibria.

Special problems or courses arranged to meet the emerging needs of undergraduate students. Topics have included AIChE's annual Chem-E-Car Competition. May be repeated for credit, as content may vary. Grading scheme at instructor's discretion.

Offered to B.S. candidates in chemistry. Units in accordance with work accomplished. Prerequisite: consent of research supervisor. Experimental and theoretical research requiring a report containing an appropriate description of the research work.

Research in chemical engineering offered as an elective in any term. Graded pass/fail.

Occasional advanced work involving reading assignments and a report on special topics. No more than 12 units in Ch 81 may be used as electives in the chemistry option.

Three terms of Ch 82 are to be completed during the junior and/or senior year of study. At the end of the third term, students enrolled in Ch 82 will present a thesis of approximately 20 pages (excluding figures and references) to the mentor and the Chemistry Curriculum and Undergraduate Studies Committee. The thesis must be approved by both the research mentor and the CUSC. An oral thesis defense will be arranged by the CUSC in the third term for all enrollees. The first two terms of Ch 82 will be taken on a pass/fail basis, and the third term will carry a letter grade.

Training in the techniques of oral presentation of chemical and biochemical topics. Practice in the effective organization and delivery of technical reports before groups. Strong oral presentation is an essential skill for successful job interviews and career advancement. Graded pass/fail. Class size limited to 12 students.

A research project carried out under the mentorship of an approved faculty member. Before the beginning of the first term of the thesis, students must submit a proposal - with project details and significant design component clearly defined - for review and approval by the thesis mentor and chemical engineering senior thesis coordinator (Option Rep). In addition, students must submit the following to the thesis mentor and chemical engineering senior thesis coordinator: a midterm progress report in each term; end-of-term progress reports at the end of the first two terms; and a thesis draft in the third term. A grade will not be assigned prior to completion of the thesis, which normally takes three terms. A P grade will be given for the first two terms and then changed to the appropriate letter grade at the end of the course.

Training in the writing of scientific research papers for chemists and chemical engineers. Fulfills the Institute scientific writing requirement.

Small group study and discussion on special areas of chemistry, chemical engineering, molecular biology, or biophysics. Instructors drawn from advanced graduate students and postdoctoral staff will lead weekly tutorial sessions and assign short homework assignments, readings, or discussions. Tutorials to be arranged with instructors before registration.

Elements of chemical kinetics and chemically reacting systems. Homogeneous and heterogeneous catalysis. Chemical reactor analysis.

Structure and bonding of inorganic species with special emphasis on symmetry, spectroscopy, oxidation-reduction reactions, organometallic, and solid-state chemistry.

A rigorous development of the basic differential equations of conservation of momentum, energy, and mass in fluid systems. Solution of problems involving fluid flow, heat transfer, and mass transfer.

A survey of selected topics beyond introductory organic chemistry, including reaction mechanisms and catalysis.

Analysis of linear dynamic systems. Feedback control. Stability of closed-loop control systems. Root locus, Frequency response, and Nyquist analysis. Feedforward, cascade, and multivariable control systems.

Lectures and recitation introducing the molecular basis of life processes. In the first term, topics will include the structure and chemical properties of biological macromolecules, molecular biology methods, and biological catalysis. The second term will cover an overview of metabolism and the biochemistry behind the transmission of genetic information.

Lectures and recitation on the molecular basis of biological structure and function. Emphasizes the storage, transmission, and expression of genetic information in cells. Specific topics include DNA replication, recombination, repair and mutagenesis, transcription, RNA processing, and chromatin structure.

Examines the Earth's resources including fresh water, nitrogen, carbon and other biogeochemical cycles that impose planetary constraints on engineering; systems approaches to sustainable development goals; fossil fuel formation, chemical composition, production and use; engineering challenges and opportunities in decarbonizing energy, transportation and industry; global flows of critical elements used in zero-carbon energy systems; food-water-energy nexus; analysis of regional and local systems to model effects of human activities on air, water and soil.

Introduction to group theory, ligand field theory, and bonding in coordination complexes and organotransition metal compounds. Systematics of bonding, reactivity, and spectroscopy of commonly encountered classes of transition metal compounds.

This course combines three parts. First, it will cover fundamental aspects of kinetics, mass-transport, and fluid physics that are relevant to microfluidic systems. Second, it will provide an understanding of how new technologies are invented and reduced to practice. Finally, students in the course will work together to design microfluidic systems that address challenges in Global Health, with an emphasis on students' inventive contributions and creativity. Students will be encouraged and helped, but not required, to develop their inventions further by working with OTT and entrepreneurial resources on campus. Participants in this course benefit from enrollment of students with diverse backgrounds and interests. For chemical engineers, suggested but not required courses are ChE 101 (Chemical Reaction Engineering) and ChE 103 abc (Transport Phenomena). Students are encouraged to contact the instructor to discuss enrollment.

Discussion of the fundamentals and applications of electrochemistry with an emphasis on the structure of electrode-electrolyte interfaces, mechanisms by which charge is transferred across it, kinetics of mass transfer to the interface, experimental techniques used to study electrode reactions, and application of electrochemical techniques to study materials chemistry. Topics may vary but usually include electrochemical thermodynamics, potential step waveforms, the electrical double layer, charge transfer kinetics, mass transfer kinetics, voltammetry, chronocoulometry, EIS, and RDE.

Short-term, open-ended projects that require students to design a chemical process or product. Each team generates and filters ideas, identifies use cases and objectives, evaluates and selects a design strategy, develops a project budget, schedules milestones and tasks, and writes a proposal with supporting documentation. Each project must meet specified requirements for societal impact, budget, duration, person hours, environmental impact, safety, and ethics.

Modern ideas of chemical bonding, with an emphasis on qualitative concepts useful for predictions of structures, energetics, excited states, and properties. Part a: The quantum mechanical basis for understanding bonding, structures, energetics, and properties of materials (polymers, ceramics, metals alloys, semiconductors, and surfaces), including transition metal and organometallic systems with a focus on chemical reactivity. The emphasis is on explaining chemical, mechanical, electrical, and thermal properties of materials in terms of atomistic concepts. Part b: The student does an individual research project using modern quantum chemistry computer programs to calculate wavefunctions, structures, and properties of real molecules.

Short-term, open-ended projects that require students to design and build a chemical process or manufacture a chemical product. Each team selects a project after reviewing a collection of proposals. Students use chemical engineering principles to design, build, test, and optimize a system, component, or product that fulfills specified performance requirements, subject to constraints imposed by budget, schedule, logistics, environmental impact, safety, and ethics.

Application of Atomistic-based methods [Quantum Mechanics (QM) and Molecular Dynamics (MD)] for predicting the structures and properties of molecules and solids and simulating the dynamical properties. This course emphasizes hands-on use of modern commercial software (such as Jaguar for QM, VASP for periodic QM, and LAMMPS for MD) for practical applications and is aimed at experimentalists and theorists interested in understanding structures, properties, and dynamics in such areas as biological systems (proteins, DNA, carbohydrates, lipids); polymers (crystals, amorphous systems, co-polymers); semiconductors (group IV, III-V, surfaces, defects); inorganic systems (ceramics, zeolites, superconductors, and metals); organo-metallics, and catalysis (heterogeneous, homogeneous, and electrocatalysis). Ch 121 a covers the basic methods with hands-on applications to systems of interest using modern software. The homework for the first 5 weeks emphasizes computer-based solutions. For the second 5 weeks of the homework each student proposes a short research project and uses atomistic simulations to solve it. Ch 121 b each student selects a more extensive research project and uses atomistic simulations to solve it.

This course provides an introduction to small molecule X-ray crystallography. Topics include symmetry, space groups, diffraction by crystals, the direct and reciprocal lattice, Patterson and direct methods for phase determination, and structure refinement. It will cover both theoretical and applied concepts and include hands-on experience in data collection, structure solution and structure refinement.

A treatment of quantum mechanics with application to molecular and material systems. The basic elements of quantum mechanics, the electronic structure of atoms and molecules, the interactions of radiation fields and matter, and time dependent techniques relevant to spectroscopy will be covered. The course sequence prepares students for Ch 225 and 226.

Short-term projects that require students to work in teams to design systems or system components. Projects typically include unit operations and instruments for chemical detection. Each team must identify specific project requirements, including performance specifications, costs, and failure modes. Students use chemical engineering principles to design, implement, and optimize a system (or component) that fulfills these requirements, while addressing issues and constraints related to environmental impact, safety, and ethics. Students also learn professional ethics through the analysis of case studies.

A survey course in the properties of nuclei, and in atomic phenomena associated with nuclear-particle detection. Topics include rates of production and decay of radioactive nuclei; interaction of radiation with matter; nuclear masses, shapes, spins, and moments; modes of radioactive decay; nuclear fission and energy generation. Given in alternate years; offered 2022-23.

Short-term, open-ended research projects targeting chemical processes and materials. Each student is required to design, construct, and troubleshoot her/his own process, then use chemical engineering principles to experimentally evaluate and optimize process metrics or material attributes. Where possible, cost analysis is performed.

This course will cover basic optics and introduce modern optical spectroscopy principles and microscopy techniques. Topics include molecular spectroscopy, linear and nonlinear florescence microscopy, Raman spectroscopy, coherent microscopy, single-molecule spectroscopy, and super-resolution imaging.

Design, construction, and characterization of engineered biological systems. Students will propose and execute research projects in biomolecular engineering and synthetic biology. Emphasis will be on projects that apply rational or library-based design strategies to the control of system behavior.

Physical description of the structure, spectra and dynamics of molecules. Topics include: time-dependent quantum mechanics, molecular structure, coherence, path integral formalism, scattering cross sections, rate constants, intermolecular potentials, classical two-body elastic scattering, reactive scattering, nonadiabatic processes, statistical theories of unimolecular reactions, photochemistry, laser and molecular beam methods, theory of electron transfer, solvent effects, condensed phase dynamics, surface reactions, isotope effects.

The properties and photoelectrochemistry of semiconductors and semiconductor/liquid junction solar cells will be discussed. Topics include optical and electronic properties of semiconductors; electronic properties of semiconductor junctions with metals, liquids, and other semiconductors, in the dark and under illumination, with emphasis on semiconductor/liquid junctions in aqueous and nonaqueous media. Problems currently facing semiconductor/liquid junctions and practical applications of these systems will be highlighted. Part b not offered 2022-23.

Through short lectures, in-class activities, and problem sets, students learn and use methods in data science to complete projects focused on (i) descriptive and predictive analyses of chemical processes and (ii) Quantitative Structure Property Relationships (QSPR). Topics covered may include six sigma; SPC & SQC; time-series analysis; data preprocessing; dimensionality reduction; supervised, reinforcement, and unsupervised learning; decision tree & clustering methods; univariate and multivariate regression; and visualization. Python is the programming language of instruction.

Student groups complete a one-term, data-science project that addresses an instructor-approved chemical engineering challenge. The project may be an original research idea; related to work by a research group at the Institute; an entry in a relevant national/regional contest; a response to an industry relationship; or other meaningful opportunity. There is no lecture, but students participate in weekly progress updates. A student may not select a project too similar to research completed to fulfill requirements for ChE 80 or ChE 90 abc.

An advanced survey of selected topics in modern organic chemistry. Topics vary from year to year and may include structural and theoretical organic chemistry; materials chemistry; macromolecular chemistry; mechanochemistry; molecular recognition/supramolecular chemistry; reaction mechanisms; reactive intermediates; pericyclic reactions; and photochemistry. Part a not offered 2022-23.

An introduction to the physics that govern the structure and dynamics of polymeric liquids, and to the physical basis of characterization methods used in polymer science. The course emphasizes the scaling aspects of the various physical properties. Topics include conformation of a single polymer, a chain under different solvent conditions; dilute and semi-dilute solutions; thermodynamics of polymer blends and block copolymers; polyelectrolytes; rubber elasticity; polymer gels; linear viscoelasticity of polymer solutions and melts.

Discussion of key principles in organic chemistry, with an emphasis on reaction mechanisms and problem-solving. This course is intended primarily for first-year graduate students with a strong foundation in organic chemistry. Meets during the first three weeks of the term. Graded pass/fail.

The foundations of heat, mass, and momentum transfer for single and multiphase fluids will be developed. Governing differential equations; laminar flow of incompressible fluids at low and high Reynolds numbers; forced and free convective heat and mass transfer, diffusion, and dispersion. Emphasis will be placed on physical understanding, scaling, and formulation and solution of boundary-value problems. Applied mathematical techniques will be developed and used throughout the course.

Survey of heterogeneous reactions on metal and oxide catalysts. Langmuir-Hinshelwood versus Eley-Rideal reaction mechanisms. Reaction, diffusion, and heat transfer in heterogeneous catalytic systems. Characterization of porous catalysts.

Ch 153 a: Topics in modern inorganic chemistry. Electronic structure, spectroscopy, and photochemistry with emphasis on examples from the research literature. Ch 153 b: Applications of physical methods to the characterization of inorganic and bioinorganic species, with an emphasis on the practical application of Moessbauer, EPR, and pulse EPR spectroscopies. Ch 153 c: Theoretical and spectroscopic approaches to understanding the electronic structure of transition metal ions. Topics in the 153 bc alternate sequence may include saturation magnetization and zero-field splitting in magnetic circular dichroism and molecular magnetism, hyperfine interactions in electron paramagnetic resonance spectroscopy, Moessbauer and magnetic Moessbauer spectroscopy, vibronic interactions in electronic absorption and resonance Raman spectroscopy, and bonding analyses using x-ray absorption and/or emission spectroscopies.

A general discussion of the reaction mechanisms and the synthetic and catalytic uses of transition metal organometallic compounds. Second term: a survey of the elementary reactions and methods for investigating reaction mechanisms. Third term: contemporary topics in inorganic and organometallic synthesis, structure and bonding, and applications in catalysis. Part b not offered 2022-23.

The course introduces rational design and evolutionary methods for engineering functional protein and nucleic acid systems. Rational design topics include molecular modeling, positive and negative design paradigms, simulation and optimization of equilibrium and kinetic properties, design of catalysts, sensors, motors, and circuits. Evolutionary design topics include evolutionary mechanisms and tradeoffs, fitness landscapes and directed evolution of proteins. Some assignments require programming (Python is the language of instruction).

An introduction to the fundamentals and simple applications of statistical thermodynamics. Foundation of statistical mechanics; partition functions for various ensembles and their connection to thermodynamics; fluctuations; noninteracting quantum and classical gases; heat capacity of solids; adsorption; phase transitions and order parameters; linear response theory; structure of classical fluids; computer simulation methods.

An advanced course emphasizing the conceptual structure of modern thermodynamics and its applications. Review of the laws of thermodynamics; thermodynamic potentials and Legendre transform; equilibrium and stability conditions; metastability and phase separation kinetics; thermodynamics of single-component fluid and binary mixtures; models for solutions; phase and chemical equilibria; surface and interface thermodynamics; electrolytes and polymeric liquids.

A detailed course about chemical transformation in Earth's atmosphere. Kinetics, spectroscopy, and thermodynamics of gas-phase chemistry of the stratosphere and troposphere; sources, sinks, and lifetimes of trace atmospheric species; stratospheric ozone chemistry; oxidation mechanisms in the troposphere; aerosol chemistry.

Discussion of research fields in biochemistry and molecular biophysics at Caltech. Development of skills in literature analysis and information synthesis.

This course will cover selected aspects of the chemistry of aquatic systems. Lectures cover basic principles of physical-organic chemistry relevant to the aquatic environment under realistic conditions. Specific topics covered in Part I include the basic principles of equilibrium chemical and physical processes important natural waters. Topics include: chemical potential, fugacity, phase transfer, acid-base chemistry, metal-ligand substitution chemistry, surface chemistry, octanol-water partitioning, air-water partitioning, partitioning to solid organic matter and biomedia, sorption processes, air-water exchange dynamics, and the kinetics and mechanisms of coupled organic and inorganic redox reactions. Thermodynamics, transport, phase transfer and kinetics are emphasized.

This course will cover selected aspects of the organic chemistry of aquatic systems and coupled air-water systems. Topics include photochemical transformations, biochemical transformations in sub-surface water, surface water, and sediments, heterogeneous surface reactions and catalysis, hydrolysis reactions, nucleophilic displacement and substitution reactions, elimination reactions, carboxylic acid ester hydrolysis, thiophosphoric acid ester hydrolysis, carbamate ester hydrolysis, and amide ester hydrolysis. The primary goal is to better understand factors controlling the fate and behavior of organic compounds and persistent organic pollutants in the global environment. Case studies will be presented.

Discussion of the energetic principles and molecular mechanisms that underlie enzyme's catalytic proficiency and exquisite specificity. Principles of allostery, selectivity, and enzyme evolution. Practical kinetics and their application to more complex biological systems, including steady-state and pre-steady-state kinetics, kinetic simulations, and kinetics at single molecule resolution.

Offered to M.S. candidates in chemistry. Graded pass/fail.

This course will cover the basic principles of biological and medical imaging technologies including magnetic resonance, ultrasound, nuclear imaging, fluorescence, bioluminescence and photoacoustics, and the design of chemical and biological probes to obtain molecular information about living systems using these modalities. Topics will include nuclear spin behavior, sound wave propagation, radioactive decay, photon absorption and scattering, spatial encoding, image reconstruction, statistical analysis, and molecular contrast mechanisms. The design of molecular imaging agents for biomarker detection, cell tracking, and dynamic imaging of cellular signals will be analyzed in terms of detection limits, kinetics, and biological effects. Participants in the course will develop proposals for new molecular imaging agents for applications such as functional brain imaging, cancer diagnosis, and cell therapy.

Special courses of readings or laboratory instruction. The student should consult a member of the faculty and prepare a definite program of reading, computation, theory and/or experiment. The student must submit a summary of progress at midterm and, at the end of the quarter, a final assignment designed in consultation with the instructor. This course may be credited only once. Grading: either grades or pass/fail, as arranged with the instructor.

The course focuses on a seminar on selected topics from outside faculty on recent advances in biochemistry. Components for each faculty visit include participation in a recitation, a formal discussion section with visiting faculty, and attendance of the Biochemistry seminar. Biochemistry Seminars take place 1-2 times per month (usually 4pm on Thursdays).

A tutorial course of problem solving in the more advanced aspects of ligand field theory. Recommended only for students interested in detailed theoretical work in the inorganic field.

Quantum mechanical foundations of optical spectroscopy as applied to chemical and material systems. Topics include optical properties of materials, nonlinear and quantum optics, and multidimensional spectroscopy.

Advanced course in macromolecular crystallography integrating lecture and laboratory treatment of diffraction theory, crystallization (proteins, nucleic acids and macromolecular complexes), crystal characterization, X-ray sources and optics, crystal freezing, X-ray diffraction data collection (in-house and synchrotron), data reduction, multiple isomorphous replacement, single- and multi-wavelength anomalous diffraction phasing techniques, molecular replacement, electron density interpretation, structure refinement, structure validation, coordinate deposition and structure presentation. In the laboratory component, one or more proteins will be crystallized and the structure(s) determined by several methods, in parallel with lectures on the theory and discussions of the techniques.

An integrated approach to synthetic problem solving featuring an extensive review of modern synthetic reactions with concurrent development of strategies for synthesis design. Part a will focus on the application of modern methods of stereocontrol in the construction of stereochemically complex acyclic systems. Part b will focus on strategies and reactions for the synthesis of cyclic systems.

By arrangement with members of the faculty, properly qualified graduate students will have the opportunity to engage in a short-term research project culminating in a presentation to their peers enrolled in the course and participating laboratories. (Pass-Fail only).

By arrangement with members of the faculty, properly qualified graduate students are directed in research in chemistry.

Offered to Ph.D. candidates in chemical engineering. Main lines of research now in progress are covered in detail in section two.