Each memory module is unique; no two (or more) modules will be EXACTLY alike.
Why? Because of component tolerance (value) variations, and on the method and quality of assembly of components, each module will have their own unique characteristics.
In order for two (or more) modules to work together (properly) in a system, each module characteristic MUST have similar characteristics to the other module(s). If module characteristics are close enough/almost identical, then dual channel operation will be available provided the modules are inserted in the correct slots. If module characteristics are fairly close in characteristics, but not quite close enough, then the modules may only run in single channel mode. If the module characteristics are too far apart with respect to each other, then the system may not even boot, or it may crash etc.
To ensure module compatibility with each other, it is usually recommended to get dual (triple, or quad) channel kits where the modules have been tested and selected for best compatibility due to similar characteristics.
So if wanting to add another (single) module to the system, there is some risk that the new module characteristics may not be compatible with existing module characteristics, and the system may not boot, might crash, freeze etc. But if lucky, the new module characteristics might be close enough to the existing module characteristics to allow successful/compatible operation of the modules.
But if the new module does not work with the existing module, then it will have to be returned and replaced with another, and so on until compatible memory combination is found.
Also having same or balanced memory capacity for each module ensures full dual channel operation for all of the memory. If using one 2 GB module and a 4 GB module, which just happens to have similar characteristics to the 2 GB module, then the system will (probably) run as a combination of dual and single channel modes; the first 2 GB of 4 GB module will be dual channel with the 2 GB module, and the remaining 2 GB of the 4 GB module will be single channel operation. This is not as ideal as FULL dual channel operation.
To avoid these issues, it is recommended that a dual channel kit be purchased (either 2 x 2 GB, or 2 x 4 GB). The advantage is that full dual channel operation will be enabled which maximizes available memory bandwidth. The existing memory module could be kept as a backup or sell it.